Acrylic dispersing agents in nanocomposites

ABSTRACT

The instant invention discloses a composition, preferably a nanocomposite material, comprising (a) a synthetic polymer, (b) a filler such as for example a natural or synthetic phyllosilicate or a mixture of such phyllosilicates, preferably in nanoparticles, and (c) as dispersing agent a polymer based on a long chain alkyl meth(acryte).

The present invention relates to a composition, preferably ananocomposite material, comprising (a) a synthetic polymer, especially apolyolefin, (b) a filler, especially a natural or syntheticphyllosilicate or a mixture of such phyllosilicates, preferably innanoparticles, and (c) as dispersing agent a polymer based on a longchain alkyl meth(acrylate), preferably a statistical, block or combcopolymer having at least one hydrophilic and at least one hydrophobicsegment which is based on a long chain alkyl acrylate. The presentinvention relates also to a process for the preparation of a syntheticpolymer nanocomposite material which comprises melt mixing a mixture ofa) a synthetic polymer, b) a filler, and c) as dispersing agent apolymer based on a long chain alkyl meth(acrylate) and to the use of thelatter to intercalate and exfoliate a filler and disperse the filler ina synthetic polymer matrix to form a nanocomposite material.

The addition of fillers to organic materials, especially polymers, isknown and is described for example in Hans Zweifel (editor), PlasticsAdditives Handbook, 5th Edition, pages 901-948, Hanser Publishers,Munich 2001. The use of fillers in polymers has the advantage that it ispossible to bring about improvement in, for example, the mechanicalproperties, especially the density, hardness, rigidity (modulus) orreduced shrinkage of the polymer.

Using extremely small filler particles (<200 nm), so-called nano-scaledfillers, mechanical properties, heat distortion temperature stability orflame retardant property of the polymers can be improved at a much lowerconcentration typically of 2 to 10% by weight compared to 20 to 50% byweight with the micro-scaled normal filler particles. Polymerscontaining nano-scaled fillers combine favourable mechanical propertieslike strength, modulus and impact, and show improved surface qualitieslike gloss, lower tool wear at processing and better conditions forrecycling. Coatings and films comprising nano-scaled fillers showimproved stability, flame retardance, gas barrier properties and scratchresistance.

Nano-scaled fillers possess an extremely large surface with high surfaceenergy. The deactivation of the surface energy and the compatibilizationof the nano-scaled fillers with a polymeric substrate is, therefore,even more important than with a common micro-scaled filler in order toavoid aggregation during processing or conversion of the filled polymerand to reach an excellent dispersion of the nano-scaled filler in thefinal article.

There is a substantial recent literature on organic-inorganicnanocomposites based on clays or layered silicates such asmontmorillonite and synthetic polymers. Polyolefin nanocomposites havebeen prepared from organic modified days. The clays used are generallymodified with alkyl or dialkyl ammonium ions or amines or in a few casesother onium ions, like for example phosphonium. The ammonium ion/amineadditives are usually incorporated into the day structure by a separatesolution intercalation step.

These conventional organic modified days have a number of disadvantageswhen used for the preparation of polyolefin nanocomposites. Ammoniumsalts are thermally unstable at temperatures used in polyolefinprocessing or may be otherwise reactive under processing conditions.These instabilities result in poor processing stability, inferiormechanical properties, discoloration, odor formation and reducedlong-term stability in addition to the formation of volatileby-products.

In order to improve the polyolefin nanocomposite formation by meltprocessing the use of an additional compatibilizer has been proposed,most often a maleic anhydride grafted polypropylene, which in workingexamples is present as major component of the final product.

M. Kawasumi et al., Macromolecules 1997, 30, 6333-6338 or U.S. Pat. No.5,973,053 disclose that a polypropylene nanocomposite is obtained when aday, premodified with octadecylammonium salts, is compounded withpolypropylene in the presence of polyolefin oligomers containing polarfunctionality, for example maleic anhydride grafted polypropylene.

Although compatibilizers can improve the stability of nanocompositesmainly with regard to avoiding agglomeration of the filler, the otherweaknesses of the nanocomposites are not improved.

It has now been found that improved synthetic polymer materials with abetter long term thermostability, with reduced odor and reducedundesired discoloration, which occurs as a result of the decompositionof the modification agents, can be prepared by the use of a polymer thatcomprises at least one segment which is based on a long chain alkylmeth(acrylate).

The present invention therefore provides a composition comprising

-   -   a) a synthetic polymer,    -   b) a filler, and    -   c) as dispersing agent a polymer based on a long chain alkyl        meth(acrylate).

Preferably, component (c) is a statistical, block or comb copolymerhaving at least one segment which is based on a long chain alkylmeth(acrylate).

Of interest is also a composition wherein component (c) is astatistical, block or comb copolymer having at least one hydrophilic andat least one hydrophobic segment which is based on a long chain alkylacrylate.

Of special interest is a composition wherein component (c) is astatistical, block or comb copolymer having at least 10-100% (mol %)segments based on a long chain alkyl meth(acrylate).

Preferably, component (b) is a filler in nanoparticles (nano-scaledfiller or nanoparticulate filler).

Of special interest is a composition wherein component (b) is ananoparticulate filler which is not organically modified.

Component (c) is suitable for intercalating and exfoliating a filler anddisperse the filler in a synthetic polymer matrix, especially athermoplastic polymer, to form a nanocomposite material.

Examples of such synthetic polymers are:

1. Polymers of monoolefins and diolefins, for example polypropylene,polyisobutylene, polybut-1-ene, poly-4-methylpent-1-ene,polyvinylcyclohexane, polyisoprene or polybutadiene, as well as polymersof cycloolefins, for instance of cyclopentene or norbornene,polyethylene (which optionally can be crosslinked), for example highdensity polyethylene (HDPE), high density and high molecular weightpolyethylene (HDPE-HMW), high density and ultrahigh molecular weightpolyethylene (HDPE-UHMW), medium density polyethylene (MDPE), lowdensity polyethylene (LDPE), linear low density polyethylene (LLDPE),(VLDPE) and (ULDPE).

Polyolefins, i.e. the polymers of monoolefins exemplified in thepreceding paragraph, preferably polyethylene and polypropylene, can beprepared by different, and especially by the following, methods:

-   -   a) radical polymerisation (normally under high pressure and at        elevated temperature).    -   b) catalytic polymerisation using a catalyst that normally        contains one or more than one metal of groups IVb, Vb, VIb or        VIII of the Periodic Table. These metals usually have one or        more than one ligand, typically oxides, halides, alcoholates,        esters, ethers, amines, alkyls, alkenyls and/or aryls that may        be either π- or σ-coordinated. These metal complexes may be in        the free form or fixed on substrates, typically on activated        magnesium chloride, titanium(III) chloride, alumina or silicon        oxide. These catalysts may be soluble or insoluble in the        polymerisation medium. The catalysts can be used by themselves        in the polymerisation or further activators may be used,        typically metal alkyls, metal hydrides, metal alkyl halides,        metal alkyl oxides or metal alkyloxanes, said metals being        elements of groups Ia, IIa and/or IIIa of the Periodic Table.        The activators may be modified conveniently with further ester,        ether, amine or silyl ether groups. These catalyst systems are        usually termed Phillips, Standard Oil Indiana, Ziegler (-Natta),        TNZ (DuPont), metallocene or single site catalysts (SSC).

2. Mixtures of the polymers mentioned under 1), for example mixtures ofpolypropylene with polyisobutylene, polypropylene with polyethylene (forexample PP/HDPE, PP/LDPE) and mixtures of different types ofpolyethylene (for example LDPE/HDPE).

3. Copolymers of monoolefins and diolefins with each other or with othervinyl monomers, for example ethylene/propylene copolymers, linear lowdensity polyethylene (LLDPE) and mixtures thereof with low densitypolyethylene (LDPE), propylene/but-1-ene copolymers,propylene/isobutylene copolymers, ethylene/but-1-ene copolymers,ethylene/hexene copolymers, ethylene/methylpentene copolymers,ethylene/heptene copolymers, ethylene/octene copolymers,ethylene/vinylcyclohexane copolymers, ethylene/cycloolefin copolymers(e.g. ethylene/norbornene like COC), ethylene/1-olefins copolymers,where the 1-olefin is generated in-situ; propylene/butadiene copolymers,isobutylene/isoprene copolymers, ethylene/vinylcyclohexene copolymers,ethylene/alkyl acrylate copolymers, ethylene/alkyl methacrylatecopolymers, ethylene/vinyl acetate copolymers or ethylene/acrylic acidcopolymers and their salts (ionomers) as well as terpolymers of ethylenewith propylene and a diene such as hexadiene, dicydopentadiene orethylidene-norbornene; and mixtures of such copolymers with one anotherand with polymers mentioned in 1) above, for examplepolypropylene/ethylene-propylene copolymers, LDPE/ethylene-vinyl acetatecopolymers (EVA), LDPE/ethylene-acrylic acid copolymers (EAA),LLDPE/EVA, LLDPE/EAA and alternating or random polyalkylene/carbonmonoxide copolymers and mixtures thereof with other polymers, forexample polyamides.

4. Hydrocarbon resins (for example C₅-C₉) including hydrogenatedmodifications thereof (e.g. tackifiers) and mixtures of polyalkylenesand starch.

Homopolymers and copolymers from 1.)-4.) may have any stereostructureincluding syndiotactic, isotactic, heterotactic or atactic; whereatactic polymers are preferred. Stereoblock polymers are also included.

5. Polystyrene, poly(p-methylstyrene), poly(α-methylstyrene).

6. Aromatic homopolymers and copolymers derived from vinyl aromaticmonomers including styrene, α-methylstyrene, all isomers of vinyltoluene, especially p-vinyltoluene, all isomers of ethyl styrene, propylstyrene, vinyl biphenyl, vinyl naphthalene, and vinyl anthracene, andmixtures thereof. Homopolymers and copolymers may have anystereostructure including syndiotactic, isotactic, hemi-isotactic oratactic; where atactic polymers are preferred. Stereoblock polymers arealso included.

6a. Copolymers including aforementioned vinyl aromatic monomers andcomonomers selected from ethylene, propylene, dienes, nitriles, acids,maleic anhydrides, maleimides, vinyl acetate and vinyl chloride oracrylic derivatives and mixtures thereof, for example styrene/butadiene,styrene/acrylonitrile, styrene/ethylene (interpolymers), styrene/alkylmethacrylate, styrene/butadiene/alkyl acrylate, styrene/butadiene/alkylmethacrylate, styrene/maleic anhydride, styrene/acrylonitrile/methylacrylate; mixtures of high impact strength of styrene copolymers andanother polymer, for example a polyacrylate, a diene polymer or anethylene/propylene/diene terpolymer; and block copolymers of styrenesuch as styrene/butadiene/styrene, styrene/isoprene/styrene,styrene/ethylene/butylene/styrene or styrene/ethylene/propylene/styrene.

6b. Hydrogenated aromatic polymers derived from hydrogenation ofpolymers mentioned under 6.), especially includingpolycyclohexylethylene (PCHE) prepared by hydrogenating atacticpolystyrene, often referred to as polyvinylcyclohexane (PVCH).

6c. Hydrogenated aromatic polymers derived from hydrogenation ofpolymers mentioned under 6a.).

Homopolymers and copolymers may have any stereostructure includingsyndiotactc, isotactic, hemi-isotactic or atactic; where atacticpolymers are preferred. Stereoblock polymers are also included.

7. Graft copolymers of vinyl aromatic monomers such as styrene or(X-methylstyrene, for example styrene on polybutadiene, styrene onpolybutadiene-styrene or polybutadiene-acrylonitrile copolymers; styreneand acrylonitrile (or methacrylonitrile) on polybutadiene; styrene,acrylonitrile and methyl methacrylate on polybutadiene; styrene andmaleic anhydride on polybutadiene; styrene, acrylonitrile and maleicanhydride or maleimide on polybutadiene; styrene and maleimide onpolybutadiene; styrene and alkyl acrylates or methacrylates onpolybutadiene; styrene and acrylonitrile on ethylene/propylene/dieneterpolymers; styrene and acrylonitrile on polyalkyl acrylates orpolyalkyl methacrylates, styrene and acrylonitrile on acrylate/butadienecopolymers, as well as mixtures thereof with the copolymers listed under6), for example the copolymer mixtures known as ABS, MBS, ASA or AESpolymers.

8. Halogen-containing polymers such as polychloroprene, chlorinatedrubbers, chlorinated and brominated copolymer of isobutylene-isoprene(halobutyl rubber), chlorinated or sulfo-chlorinated polyethylene,copolymers of ethylene and chlorinated ethylene, epichlorohydrin homo-and copolymers, especially polymers of halogen-containing vinylcompounds, for example polyvinyl chloride, polyvinylidene chloride,polyvinyl fluoride, polyvinylidene fluoride, as well as copolymersthereof such as vinyl chloride/vinylidene chloride, vinyl chloride/vinylacetate or vinylidene chloride/vinyl acetate copolymers.

9. Polymers derived from α,β-unsaturated acids and derivatives thereofsuch as polyacrylates and polymethacrylates; polymethyl methacrylates,polyacrylamides and polyacrylonitriles, impact-modified with butylacrylate.

10. Copolymers of the monomers mentioned under 9) with each other orwith other unsaturated monomers, for example acrylonitrile/butadienecopolymers, acrylonitrile/alkyl acrylate copolymers,acrylonitrile/alkoxyalkyl acrylate or acrylonitrile/vinyl halidecopolymers or acrylonitrile/alkyl methacrylate/butadiene terpolymers.

11. Polymers derived from unsaturated alcohols and amines or the acylderivatives or acetals thereof, for example polyvinyl alcohol, polyvinylacetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate,polyvinyl butyral, polyallyl phthalate or polyallyl melamine; as well astheir copolymers with olefins mentioned in 1) above.

12. Homopolymers and copolymers of cyclic ethers such as polyalkyleneglycols, polyethylene oxide, polypropylene oxide or copolymers thereofwith bisglycidyl ethers.

13. Polyacetals such as polyoxymethylene and those polyoxymethyleneswhich contain ethylene oxide as a comonomer; polyacetals modified withthermoplastic polyurethanes, acrylates or MBS.

14. Polyphenylene oxides and sulfides, and mixtures of polyphenyleneoxides with styrene polymers or polyamides.

15. Polyurethanes derived from hydroxyl-terminated polyethers,polyesters or polybutadienes on the one hand and aliphatic or aromaticpolyisocyanates on the other, as well as precursors thereof.

16. Polyamides and copolyamides derived from diamines and dicarboxylicacids and/or from aminocarboxylic acids or the corresponding lactams,for example polyamide 4, polyamide 6, polyamide 6/6, 6/10, 6/9, 6/12,4/6, 12/12, polyamide 11, polyamide 12, aromatic polyamides startingfrom m-xylene diamine and adipic acid; polyamides prepared fromhexamethylenediamine and isophthalic or/and terephthalic acid and withor without an elastomer as modifier, for examplepoly-2,4,4,-trimethylhexamethylene terephthalamide or poly-m-phenyleneisophthalamide; and also block copolymers of the aforementionedpolyamides with polyolefins, olefin copolymers, lonomers or chemicallybonded or grafted elastomers; or with polyethers, e.g. with polyethyleneglycol, polypropylene glycol or polytetramethylene glycol; as well aspolyamides or copolyamides modified with EPDM or ABS; and polyamidescondensed during processing (RIM polyamide systems).

17. Polyureas, polyimides, polyamide-imides, polyetherimids,polyesterimids, polyhydantoins and polybenzimidazoles.

18. Polyesters derived from dicarboxylic acids and diols and/or fromhydroxycarboxylic acids or the corresponding lactones, for examplepolyethylene terephthalate, polybutylene terephthalate,poly-1,4-dimethylolcyclohexane terephthalate, polyalkylene naphthalate(PAN) and polyhydroxybenzoates, as well as block copolyether estersderived from hydroxyl-terminated polyethers; and also polyestersmodified with polycarbonates or MBS.

19. Polycarbonates and polyester carbonates.

20. Polyketones.

21. Polysulfones, polyether sulfones and polyether ketones.

22. Crosslinked polymers derived from aldehydes on the one hand andphenols, ureas and melamines on the other hand, such asphenol/formaldehyde resins, urea/formaldehyde resins andmelamine/formaldehyde resins.

23. Drying and non-drying alkyd resins.

24. Unsaturated polyester resins derived from copolyesters of saturatedand unsaturated dicarboxylic acids with polyhydric alcohols and vinylcompounds as crosslinking agents, and also halogen-containingmodifications thereof of low flammability.

25. Crosslinkable acrylic resins derived from substituted acrylates, forexample epoxy acrylates, urethane acrylates or polyester acrylates.

26. Alkyd resins, polyester resins and acrylate resins crosslinked withmelamine resins, urea resins, isocyanates, isocyanurates,polyisocyanates or epoxy resins.

27. Crosslinked epoxy resins derived from aliphatic, cycloaliphatic,heterocyclic or aromatic glycidyl compounds, e.g. products of diglycidylethers of bisphenol A and bisphenol F, which are crosslinked withcustomary hardeners such as anhydrides or amines, with or withoutaccelerators.

28. Blends of the aforementioned polymers (polyblends), for examplePP/EPDM, Polyamide/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS,PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/acrylates, POM/thermoplastic PUR,PC/thermoplastic PUR, POM/acrylate, POM/MBS, PPO/HIPS, PPO/PA 6.6 andcopolymers, PA/HDPE, PA/PP, PA/PPO, PBT/PC/ABS or PBT/PET/PC.

The synthetic polymers to be protected are preferably thermoplasticpolymers, especially polyolefins, polystyrenes, polyamides, polyesters,polyacrylates, most preferably polyolefins, in particular polyethyleneand polypropylene or copolymers thereof with mono- and diolefins.

Preferred fillers are for example natural or synthetic phyllosilicatesor a mixture of such phyllosilicates. Fillers of special interest arefor example layered silicate clays. Of very special interest arecompositions comprising as component (b) a montmorillonite, bentonite,beidelite, mica, hectorite, saponite, nontronite, sauconite,vermiculite, ledikite, magadite, kenyaite, stevensite, volkonskoite,hydrotalcite, illite, kaolinite, wollastonite, attapulgite, talc orsilica or a mixture thereof.

Component (b) can be unmodified or modified by a modification agent suchas, for example, an ammonium, an amine, a phosphonium, sulfonium orsilane compound.

Examples of modification agents for nano-clays are for example:

1. Amine and ammonium compounds, for example, distearyidimethylammoniumchloride, stearylbenzyldimethylammonium chloride, stearylamine,stearyidiethoxyamine or aminododecanoic acid [commercially available asNanofil® from Südchemie, Germany]; dimethyl ditallow ammonium,trioctylmethyl ammonium, dipolyoxyethylenealkylmethyl ammonium orpolyoxypropylenemethyldiethyl ammonium [commercially available asmodified Somasif® from CO-OP Chemical]; octadecylamine,triethoxysilanyl-propylamine [commercially available as Nanomer® fromNanocor], polyalkoxylated ammonium compounds such as for exampleoctadecyl bis(polyoxyethylene[15]amine [Ethomeen® from Eastman] oroctadecyl methyl bis(polyoxyethylene[15]ammonium chloride [Etoquad® fromEastman] or just the corresponding free amines.

2. Phosphonium compounds, for example tetrabutylphosphonium or octadecyltriphenyl phosphonium [commercially available from Eastman].

3. Others, for example, triethoxyoctylsilane [commercially available asNanomer® from Nanocor], ammonium, sulfonium or pyridium compounds asdisclosed for example in WO-A-01/04050 or WO-A-99167790; block or graftcopolymers such as for example PEO-b-PS or poly-4-vinylpyridine-b-PS; orsolvents for swelling such as for example γ-butyrolactone,2-pyrrolidone, dimethylsulfoxide, diglyme, tetrahydrofuran or furfurylalcohol.

Compositions which are of interest include those comprising as component(c) an acrylic copolymer. Of special interest are compositions whereincomponent (c) contains an acrylate or methacrylate comprising at least 8methylene groups in the side chain. Also of interest are compositionswherein component (c) contains a C₁₂-C₃₂alkyl meth(acrylate), forexample stearyl or octadecyl acrylate (ODA) or methacrylate (ODMA).

Alkyl having between 8 and 32 carbon atoms is a branched or unbranchedradical, for example octyl, decyl, 1-methylundecyl, dodecyl, tridecyl,tetradecyl, pentadecyl, hexadecyl, heptadecyl or octadecyl.

Surprisingly, we have found that homopolymers based on long chain(meth)acrylates and their copolymers with short chain (meth)acrylatesare effective as well.

An example of a preferred homopolymer is poly(octadecyl acrylate). Anexample of a preferred copolymer is poly((octadecylmethacrylate)-co-(methyl acrylate)).

Of special interest are compositions comprising as component (c)poly(octadecyl acrylate)-co-(maleic anhydride), poly(octadecylacrylate)-co-(poly(ethylene glycol)methyl ether acrylate),poly(octadecyl acrylate)-co-(diethylene glycol ethyl ether acrylate),poly(octadecyl acrylate)-co-(N-vinylpyrrolidone), poly(octadecylmethacrylate)-co-(N-vinylpyrrolidone), poly-(octadecylmethacrylate)-co-(maleic anhydride), poly(octadecylacrylate)-co-(glycidyl acrylate), poly(octadecylacrylate)-co-(2-dimethylaminoethyl acrylate), poly(octadecylacrylate)-co-(poly(ethylene glycol)methyl ether acrylate),poly(octadecyl acrylate)-co-(diethylene glycol ethyl ether acrylate),poly(octadecyl acrylate)-co-(methacrylolyoxyethyl phosphate),poly(lauryl acrylate)-co-(maleic anhydride), poly(octadecylacrylate)-co-(glycidyl methacrylate) or poly(octadecylacrylate)-co-(methacrylic acid),

The statistical, block or comb copolymer having at least one segmentwhich is based on a long chain alkyl meth(acrylate) can be prepared bydifferent methods.

These methods include conventional free radical polymerization andcontrolled or living free radical polymerization. Such controlled freeradical polymerization (CFRP) can preferally occur by four suitableroutes:

-   a1) Polymerization in the presence of alkoxyamine    initiator/regulator compounds;-   a2) Polymerization in the presence of a stable nitroxyl free radical    and a radical initiator (source of free radicals);-   a3) Polymerization under atom transfer radical polymerization    (ATRP); or-   a4) RAFT polymerization which refers to a method of polymer    synthesis by radical polymerization using chain transfer agents    which react by reversible addition—fragmentation chain transfer.

For example U.S. Pat. No. 4,581,429 or EP-A-0 621 878 discloses thepreparation of block copolymers by method a1).

For example WO-A-94/11412 discloses the preparation of block copolymersby method a2).

For example WO-A-01/51534 discloses the preparation of comb copolymersby the ATRP method a3). Kamigaito and Sawamoto in Chemical Reviews 2001,101, 3689-3745 decribe the preparation of block and other polymers bythe ATRP method a3) as well.

For example WO-A-98/01478, WO-A-99/05099 or WO-A-99/31144 disclose thepreparation of block copolymers by method a4).

The abovementioned patents are incorporated herein by reference.

An example of the application of Conv (conventional radicalpolymerization) is decribed in Example 1, an example of the applicationof NMP [nitroxide mediated polymerization, method a2) to preparepolymers suitable for use in the present invention] is decribed inExample 3, examples of the application of RAFT (polymerization withreversible addition fragmentation chain transfer, method a4) areprovided in Examples 2 (random copolymer) and 4 (block copolymer)], anexample of the application of Macroinit (conventional polymerizationwith a macroinitiator) is described in Example 5.

The synthesis of copolymers polymerization can be carried out inemulsion, solution or suspension in either a batch, semi-batch,continuous, or feed mode. In the case of living or controlled radicalpolymerization block and multi-block and gradient copolymers may beprepared by varying the rate of monomer(s) addition and/or by varyingthe sequence in which the monomer(s) are added to the polymerizationmedium. Gradient copolymers may also be prepared in a one-step processby making use of the inherent difference in reactivity of themonomer(s). For gradient block copolymers, it is often desirable to pickcomonomers with disparate reactivity ratios. For example, maleicanhydride with styrene or (meth)acrylates.

Preferably, a clay compatible segment is based on one or more monomerswhich contain polar groups such as for example ether [—O—], amide

thioamide

nitrile, hydroxy, amine, pyridine, ammonium and phosphonium inappropriate proximity. It may also be base on reactive monomerscontaining groups such as anhydride, epoxy or silane.

Preferred reactive monomers are for example PEO acrylate,1-vinyl-2-pyrrolidinone, N,N-di-methyl acrylamide, acrylonitrile, maleicanhydride, hydroxyethyl acrylate, hydroxypropyl acrylate, tert-butylα-hydroxymethacrylate, N,N′-dimethylaminoethyl acrylate,4-vinylbenzyldihydroxyethylamine, 4-vinylpyridine or4-vinylbenzyltributylphosphonium chloride.

Copolymers of the above polymers with other monomers may also be used.

The polar (hydrophilic) or “clayophilic” segments may also be derivedfrom a polar condensation or other polymers such as for examplepoly(ethylene oxide). These segments may be incorporated by making aninitiator for Conv, ATRP, NMP or RAFT derived from the condensationpolymer. The method macroinit provide an example of this approach.

Suprisingly the copolymers are little affected whether the polarsegments are introduced as single units (in a statistical copolymer) oras a sequence (in a block copolymer). Polymers prepared by controlledradical polymerization appear slightly more effective than thoseprepared by conventional polymerization. This may be due to the greaterstructural regularity (compositional homogeneity and narrowerpolydispersity) of these copolymers.

Preference is given to compositions comprising as component (c) polymersprepared by controlled or living free radical polymerization. Polymersprepared by controlled or living free radical polymerization are moreuniform in composition. It can be ensured that in copolymerization allchains contain the polar (hydrophilic), “clayophilic” or reactivefunctionality. Polymers prepared by controlled or living free radicalpolymerization are more uniform in molecular weight distribution.

It is also possible to synthesize copolymers containing long chainacrylates by esterification or transesterification of other acryliccopolymers with a long chain alcohol, for example, dodecyl alcohol oroctadecyl alcohol e.g. as disclosed in EP-A-0 386 507.

The statistical, block or comb copolymer having at least one segmentwhich is based on a long chain alkyl acrylate can also be described aspolymeric dispersing or solvating agents having amphiphilic properties.They have polar and nonpolar groups in the same molecule and they are,for example, dispersing or solvating agents based on polyethyleneglycols (PEG), polyacrylates, polysiloxanes, polyvinyl acetate or onblock copolymers containing at least one block copolymer based onacrylate, acrylic acid or methacrylate.

Most preferred copolymers for component (c) are statistical or gradientcopolymers of ODA with maleic anhydride, dimethylaminoethyl acrylate, orPEO acrylate.

Preferably, component (b) is present in the composition in an amount offrom 0.1 to 40%, in particular 0.5 to 20%, for example from 1 to 10%,based on the weight of the synthetic polymer [component (a)].

Preferably, component (c) is present in the composition in an amount offrom 0.1 to 20%, in particular 0.2 to 15%, for example from 0.2 to 10%,based on the weight of the synthetic polymer [component (a)].

Polymer nanocomposites, especially polyolefin nanocomposites, preparedwith the preferred additives in the preferred amounts possess improvedtensile modulus retained or improved tensile strength and at the sametime have a significantly improved elongation at break over systems withnano-filler alone. For example polypropylene nanocomposites according tothis invention possess greater ductility than traditional polypropylenenanocomposites prepared with organoclay and polypropylene-graft-maleicanhyfdride additive.

In addition to components (a), (b) and (c) the novel compositions maycomprise further additives, such as, for example, the following:

1. Antioxidants

1.1. Alkylated monophenols, for example2,6-di-tert-butyl-4-methylphenol, 2-butyl-4,6-di-methylphenol,2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol,2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol,2-(α-methylcyclohexyl)-4,6-di-methylphenol,2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol,2,6-di-tert-butyl-4-methoxymethylphenol, linear nonylphenols ornonylphenols branched in the side-chain, e.g. 2,6-dinonyl-methylphenol,2,4-dimethyl-6-(1′-methylundec-1′-yl)-phenol,2,4-dimethyl(1′-methylheptadec-1′-yl)-phenol,2,4-dimethyl-6-(1′-methyltridec-1′-yl)-phenol and mixtures thereof.

1.2. Alkylthiomethylphenols, for example2,4-dioctylthiomethyl-6-tert-butylphenol,2,4-dioctyl-thiomethyl-6-methylphenol,2,4-dioctylthiomethyl-6-ethylphenol,2,6-didodecylthiomethyl-4-nonylphenol.

1.3. Hydroquinones and alkylated hydroquinones, for example2,6-di-tert-butyl-4-methoxy-phenol, 2,5-di-tert-butylhydroquinone,2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octa-decyloxyphenol,2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole,3,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenylstearate, bis(3,5-di-tert-butyl-4-hydroxyphenyl) adipate.

1.4. Tocopherols, for example α-tocopherol, β-tocopherol, γ-tocopherol,δ-tocopherol and mixtures thereof (Vitamin E).

1.5. Hydroxylated thiodiphenyl ethers, for example2,2′-thiobis(6-tert-butyl-4-methylphenol), 2,2′-thiobis(4-octylphenol),4,4′-thiobis(6-tert-butyl-3-methylphenol),4,4′-thiobis(6-tert-butyl-2-methylphenol),4,4′-thiobis(3,6-di-sec-amylphenol),4,4′-bis(2,6-dimethyl-4-hydroxyphenyl) disulfide.

1.6. Alkylidene bisphenols, for example2,2′-methylenebis(6-tert-butyl-4-methylphenol),2,2′-methylenebis(6-tert-butyl-4-ethylphenol),2,2′-methylenebis[4-methyl-6-(α-methylcyclohexyl)-phenol],2,2′-methylenebis(4-methyl-6-cyclohexylphenol),2,2′-methylenebis(6-nonyl-4-methylphenol),2,2′-methylenebis(4,6-di-tert-butylphenol),2,2′-ethylidenebis(4,6-di-tert-butyl-phenol),2,2′-ethylidenebis(6-tert-butyl-4-isobutylphenol),2,2′-methylenebis[6-(α-methylbenzyl)-4-nonylphenol],2,2′-methylenebis[6-(α,α-dimethylbenzyl)-4-nonylphenol],4,4′-methylenebis(2,6-di-tert-butylphenol),4,4′-methylenebis(6-tert-butyl-2-methylphenol),1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butane,2,6-bis(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol,1,1,3-tris(5-tert-butyl-4-hydroxy-2-methylphenyl)butane,1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)-3-n-dodecylmercaptobutane,ethylene glycol bis[3,3-bis(3′-tert-butyl-4′-hydroxyphenyl)butyrate],bis(3-tert-butyl-4-hydroxy-5-methylphenyl)dicyclopentadiene,bis[2-(3′-tert-butyl-2′-hydroxy-5′-methylbenzyl)-6-tert-butyl-4-methylphenyl]terephthalate,1,1-bis(3,5-dimethyl-2-hydroxyphenyl)butane,2,2-bis(3,5-di-tert-butyl-4-hydroxyphenyl)propane,2,2-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)-4-n-dodecylmercaptobutane,1,1,5,5-tetra(5-tert-butyl-4-hydroxy-2-methylphenyl)pentane.

1.7. O- , N- and S-benzyl compounds, for example3,5,3′,5′-tetra-tert-butyl-4,4′-dihydroxy-dibenzyl ether,octadecyl-4-hydroxy-3,5-dimethylbenzyl mercaptoacetate,tridecyl-4-hydroxy-3,5-di-tert-butylbenzyl mercaptoacetate,tris(3,5-di-tert-butyl-4-hydroxybenzyl)amine,bis(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) dithioterephthalate,bis(3,5-di-tert-butyl-4-hydroxy-benzyl) sulfide,isooctyl-3,5-di-tert-butyl-4-hydroxybenzyl mercaptoacetate.

1.8. Hydroxybenzylated malonates, for example dioctadecyl2,2-bis(3,5-di-tert-butyl-2-hydroxybenzyl)malonate, dioctadecyl2-(3-tert-butyl-4-hydroxy-5-methylbenzyl)malonate,didodecylmercaptoethyl2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate,di-[4-(1,1,3,3-tetramethylbutyl)phenyl]2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate.

1.9. Hydroxybenzyl aromatic compounds, for example1,3,5-tris(3,5-di-tert-butyl-4-hydroxy-benzyl)-2,4,6-trimethylbenzene,1,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetra-methylbenzene,2,4,6-tris(3,5-di-tert-butyl 4-hydroxybenzyl)phenol.

1.10. Triazine compounds, for example2,4-bisoctylmercapto-6-(3,5-di-tert-butyl-4-hydroxy-anilino)-1,3,5-triazine,2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-tri-azine,2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,3,5-triazine,2,4,6-tris-(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,2,3-triazine,1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate,1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate,2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenylethyl)-1,3,5-triazine,1,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexahydro-1,3,5-triazine,1,3,5-tris(3,5-dicyclohexyl-4-hydroxybenzyl) isocyanurate.

1.11. Benzylphosphonates, for example dimethyl2,5-di-tert-butyl-4-hydroxybenzylphosphonate, diethyl3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl5-tert-butyl-4-hydroxy-3-methylbenzyl-phosphonate, calcium salt of3,5-di-tert-butyl-4-hydroxybenzyl-phosphonic acid monoethyl ester.

1.12. Acylaminophenols, for example 4-hydroxylauric acid anilide,4-hydroxystearic acid anilide,N-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamic acid octyl ester.

1.13. Esters of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid withmono- or poly-hydric alcohols, for example with methanol, ethanol,n-octanol, isooctanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol,ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethyleneglycol, diethylene glycol, triethylene glycol, pentaerythritol,tris(hydroxyethyl) isocyanurate, N,N′-bis(hydroxyethyl)oxalic aciddiamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

1.14. Esters of β-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acidwith mono- or poly-hydric alcohols, for example with methanol, ethanol,n-octanol, isooctanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol,ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethyleneglycol, diethylene glycol, triethylene glycol, pentaerythritol,tris(hydroxyethyl) isocyanurate, N,N′-bis(hydroxyethyl)oxalic aciddiamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane;3,9-bis[2-{3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy}-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane.

1.15. Esters of β-(3,5-dicyclohexyl-4-hydroxyphenyl)propionic acid withmono- or poly-hydric alcohols, for example with methanol, ethanol,octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol,1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethyleneglycol, triethylene glycol, pentaerythritol,tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxalic aciddiamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

1.16. Esters of 3,5-di-tert-butyl-4-hydroxyphenylacetic acid with mono-or poly-hydric alcohols, for example with methanol, ethanol, octanol,octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol,1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethyleneglycol, triethylene glycol, pentaerythritol,tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxalic aciddiamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

1.17. Amides of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid, forexampleN,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylenediamide,N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)trimethylenediamide,N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazide),N,N′-bis[2-(3-[3,5-di-tert-butyl-4-hydroxyphenyl]-propionyloxy)ethyl]oxamide(Naugard® XL-1 from Uniroyal).

1.18. Ascorbic acid (Vitamin C).

1.19. Amine-type antioxidants, for exampleN,N′-di-isopropyl-p-phenylenediamine,N,N′-di-sec-butyl-p-phenylenediamine,N,N′-bis(1,4-dimethylpentyl)-p-phenylenediamine,N,N′-bis(1-ethyl-3-methylpentyl)-p-phenylenediamine,N,N′-bis(1-methylheptyl)-p-phenylenediamine,N,N′-dicyclohexyl-p-phenylenediamine, N,N′-diphenyl-p-phenylenediamine,N,N′-di(2-naphthyl)-p-phenylenediamine,N-isopropyl-N′-phenyl-p-phenylenediamine,N-(1,3-dimethyl-butyl)-N′-phenyl-p-phenylenediamine,N-(1-methylheptyl)-N′-phenyl-p-phenylenediamine,N-cyclohexyl-N′-phenyl-p-phenylenediamine,4-(p-toluenesulfonamido)-diphenylamine,N,N′-dimethyl-N,N′-di-se-butyl-p-phenylenediamine, diphenylamine,N-allyldiphenylamine, 4-isopropoxydiphenylamine,N-phenyl-1-naphthylamine, N-(4-tert-octylphenyl)-1-naphthylamine,N-phenyl-2-naphthylamine, octylated diphenylamine, for examplep,p′-di-tert-octyl-diphenylamine, 4-n-butylaminophenol,4-butyrylaminophenol, 4-nonanoylaminophenol, 4-dodecanoylaminophenol,4-octadecanoylaminophenol, di(4-methoxyphenyl)amine,2,6-di-tert-butyl-4-dimethylaminomethylphenol,2,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane,N,N,N′,N′-tetramethyl-4,4′-diaminodiphenylmethane,1,2-di[(2-methylphenyl)amino]ethane, 1,2-di(phenylamino)propane,(o-tolyl)-biguanide, di[4-(1′,3′-dimethylbutyl)phenyl]amine,tert-octylated N-phenyl-1-naphthylamine, mixture of mono- anddi-alkylated tert-butyl-/tert-octyl-diphenylamines, mixture of mono- anddi-alkylated nonyl-diphenylamines, mixture of mono- and di-alkylateddodecyidiphenylamines, mixture of mono- and di-alkylatedisopropyl-/isohexyl-diphenylamines, mixtures of mono- and di-alkylatedtert-butyidiphenylamines, 2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine,phenothiazine, mixture of mono- and di-alkylatedtert-butyl-/tertoctyl-phenothiazines, mixture of mono- and di-alkylatedtert-octylphenothiazines, N-allylphenothiazine orN,N,N′,N′-tetraphenyl-1,4-diaminobut-2-ene.

2. UV Absorbers and Light Stabilizers

2.1. 2-(2′-Hydroxyphenyl)-benzotriazoles, for example2-(2′-hydroxy-5′-methylphenyl)-benzotriazole,2-(3′,5′-di-tert-butyl-2′-hydroxyphenyl)-benzotriazole,2-(5′-tert-butyl-2′-hydroxyphenyl)-benzotriazole,2-(2′-hydroxy-5′-(1,1,3,3-tetramethylbutyl)-phenyl)-benzotriazole,2-(3′,5′-di-tert-butyl-2′-hydroxyphenyl)-5-chlorobenzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-methylphenyl)-5-chlorobenzotriazole,2-(3′-sec-butyl-5′-tert-butyl-2′-hydroxyphenyl)-benzotriazole,2-(2′-hydroxy-4′-octyloxyphenyl)-benzotriazole,2-(3′,5′-di-tert-amyl-2′-hydroxyphenyl)-benzotriazole,2-(3′,5′-bis(α,α-dimethylbenzyl)-2′-hydroxyphenyl)-benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-octyloxycarbonylethyl)phenyl)-5-chlorobenzotriazole,2-(3′-tert-butyl-5′-[2-(2-ethylhexyloxy)carbonylethyl]-2′-hydroxyphenyl)-5-chlorobenzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-methoxycarbonylethyl)phenyl)-5-chlorobenzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-methoxycarbonylethyl)phenyl)-benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-octyloxycarbonylethyl)phenyl)-benzotriazole,2-(3′-tert-butyl-5′-[2-(2-ethylhexyloxy)carbonylethyl]-2′-hydroxyphenyl)-benzotriazole,2-(3′-dodecyl-2′-hydroxy-5′-methylphenyl)-benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-isooctyloxycarbonylethyl)-phenyl-benzotriazole,2,2′-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-benzotriazol-2-yl-phenol];transesterification product of2-[3′-tert-butyl-5′-(2-methoxycarbonylethyl)-2′-hydroxyphenyl]-benzotriazolewith polyethylene glycol 300; [R—CH₂CH₂—COO—CH₂CH₂—]₂ whereinR=3′-tert-butyl-4′-hydroxy-5′-2H-benzotriazol-2-yl-phenyl;2-[2′-hydroxy-3′-(α,α-dimethylbenzyl)-5′-(1,1,3,3-tetramethylbutyl)phenyl]-benzotriazole;2-[2′-hydroxy-3′-(1,1,3,3-tetramethylbutyl)-5′-(α,α-dimethylbenzyl)-phenyl]-benzotriazole.

2.2. 2-Hydroxybenzophenones, for example the 4-hydroxy, 4-methoxy,4-octyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2′,4′-trihydroxy or2′-hydroxy-4,4′-dimethoxy derivative.

2.3. Esters of unsubstituted or substituted benzoic acids, for example4-tert-butyl-phenyl salicylate, phenyl salicylate, octylphenylsalicylate, dibenzoylresorcinol, bis(4-tert-butylbenzoyl)resorcinol,benzoylresorcinol, 3,5-di-tert-butyl-4-hydroxybenzoic acid2,4-di-tert-butylphenyl ester, 3,5-di-tert-butyl-4-hydroxybenzoic acidhexadecyl ester, 3,5-di-tert-butyl-4-hydroxybenzoic acid octadecylester, 3,5-di-tert-butyl-4-hydroxybenzoic acid2-methyl-4,6-di-tert-butylphenyl ester.

2.4. Acrylates, for example α-cyano-β,β-diphenylacrylic acid ethyl esteror isooctyl ester, α-methoxycarbonylcinnamic acid methyl ester,α-cyano-β-methyl-p-methoxycinnamic acid methyl ester or butyl ester,α-methoxycarbonyl-p-methoxycinnamic acid methyl ester,N-(β-methoxycarbonyl-β-cyanovinyl)-2-methyl-indoline.

2.5. Nickel compounds, for example nickel complexes of2,2′-thio-bis[4-(1,1,3,3-tetramethylbutyl)phenol], such as the 1:1 or1:2 complex, optionally with additional ligands, such as n-butylamine,triethanolamine or N-cyclohexyldiethanolamine, nickel dibutyldithiocarbamate, nickel salts of4-hydroxy-3,5-di-tert-butylbenzylphosphonic acid monoalkyl esters, suchas of the methyl or ethyl ester, nickel complexes of ketoximes, such asof 2-hydroxy-4-methylphenylundecyl ketoxime, nickel complexes of1-phenyl-4-lauroyl-5-hydroxypyrazole, optionally with additionalligands.

2.6. Sterically hindered amines, for examplebis(2,2,6,6-tetramethylpiperid-4-yl) sebacate,bis(2,2,6,6-tetramethylpiperid-4-yl) succinate,bis(1,2,2,6,6-pentamethylpiperid-4-yl) sebacate,bis(1-octyloxy-2,2,6,6-tetramethylpiperid-4-yl) sebacate,n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonic acidbis(1,2,2,6,6-pentamethylpiperidyl)ester, condensation product of1-hydroxyethyl-2,2,6,6-tetramethyl-hydroxypiperidine and succinic acid,linear or cyclic condensation products ofN,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and4-tert-octylamino-2,6-dichloro-1,3,5-s-triazine,tris(2,2,6,6-tetramethylpiperidyl)nitrilo-triacetate,tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butanetetraoate,1,1′-(1,2-ethanediyl)bis(3,3,5,5-tetramethylpiperazinone),4-benzoyl-2,2,6,6-tetramethylpiperidine,4-stearyl-oxy-2,2,6,6-tetramethylpiperidine,bis(1,2,2,6,6-pentamethylpiperidyl)-2-n-butyl-2-(2-hydroxy-3,5-di-tert-butylbenzyl)malonate,3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione,bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl) sebacate,bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl) succinate, linear or cycliccondensation products ofN,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and4-morpholino-2,6-dichloro-1,3,5-triazine, condensation product of2-chloro-4,6-di(4-n-butylamino-2,2,6,6-tetramethylpiperidyl)-1,3,5-triazineand 1,2-bis(3-aminopropylamino)ethane, condensation product of2-chloro-4,6-di(4-n-butylamino-1,2,2,6,6-pentamethylpiperidyl)-1,3,5-triazineand 1,2-bis(3-aminopropylamino)-ethane,8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4,5]decane-2,4-dione,3-dodecyl-1-(2,2,6,6-tetramethyl-4-piperidyl)pyrrolidine-2,5-dione,3-dodecyl-1-(1,2,2,6,6-pentamethyl-4-piperidyl)pyrrolidine-2,5-dione,mixture of 4-hexadecyloxy- and4-stearyloxy-2,2,6,6-tetramethylpiperidine, condensation product ofN,N′-bis(2,2,6,6-tetramethyl-piperidyl)hexamethylenediamine and4-cyclohexylamino-2,6-dichloro-1,3,5-triazine, condensation product of1,2-bis(3-aminopropylamino)ethane and 2,4,6-trichloro-1,3,5-triazine and4-butylamino-2,2,6,6-tetramethylpiperidine (CAS Reg. No. [136504-96-6]);condensation product of 1,6-diaminohexane and2,4,6-trichloro-1,3,5-triazine and also N,N-dibutylamine and4-butyl-amino-2,2,6,6-tetramethylpiperidine (CAS Reg. No.[192268-64-7]);N-(2,2,6,6-tetramethyl-4-piperidyl)-n-dodecylsuccinimide,N-(1,2,2,6,6-pentamethyl-4-piperidyl)-n-dodecylsuccinimide,2-undecyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxo-spiro[4.5]decane,reaction product of7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospiro[4.5]decaneand epichlorohydrin,1,1-bis(1,2,2,6,6-pentamethyl-4-piperidyloxycarbonyl)-2-(4-methoxyphenyl)ethene,N,N′-bis-formyl-N,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine,diester of 4-methoxymethylenemalonic acid with1,2,2,6,6-pentamethyl-4-hydroxypiperidine,poly[methylpropyl-3-oxy-4-(2,2,6,6-tetramethyl-4-piperidyl)]siloxane,reaction product of maleic anhydride α-olefin copolymer and2,2,6,6-tetramethyl-4-aminopiperidine or1,2,2,6,6-pentamethyl-4-aminopiperidine.

2.7. Oxalic acid diamides, for example 4,4′-dioctyloxy oxanilide,2,2′-diethoxy oxanilide, 2,2′-dioctyloxy-5,5′-di-tert-butyl oxanilide,2,2′-didodecyloxy-5,5′-di-tert-butyl oxanilide, 2-ethoxy-2′-ethyloxanilide, N,N′-bis(3-dimethylaminopropyl)oxalamide,2-ethoxy-5-tert-butyl-2′-ethyl oxanilide and a mixture thereof with2-ethoxy-2′-ethyl-5,4′-di-tert-butyl oxanilide, mixtures of o- andp-methoxy- and also of o- and p-ethoxy-di-substituted oxanilides.

2.8. 2-(2-Hydroxyphenyl)-1,3,5-triazines, for example2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine,2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2,4-bis(2-hydroxy-4-propyl-oxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(4-methylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-tridecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-[2-hydroxy-4-(2-hydroxy-3-butyloxypropyloxy)phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-[2-hydroxy-4-(2-hydroxy-3-octyloxypropyloxy)phenyl]4,6-bis(2,4-dimethylphenyl)1,3,5-triazine,2-[4-dodecyloxy/tridecyloxy-2-hydroxypropoxy)-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-[2-hydroxy-4-(2-hydroxy-3-dodecyloxypropoxy)phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-hexyloxy)phenyl-4,6-diphenyl-1,3,5-triazine,2-(2-hydroxy-4-methoxyphenyl)-4,6-diphenyl-1,3,5-triazine,2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hydroxypropoxy)phenyl]-1,3,5-triazine,2-(2-hydroxyphenyl)-4-(4-methoxyphenyl)-6-phenyl-1,3,5-triazine,2-{2-hydroxy-4-[3-(2-ethylhexyl-1-oxy)-2-hydroxypropyloxy]phenyl}-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine.

3. Metal deactivators, for example N,N′-diphenyloxalic acid diamide,N-salicylal-N′-salicyloylhydrazine, N,N′-bis(salicyloyl)hydrazine,N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hydrazine,3-salicyloylamino-1,2,4-triazole, bis(benzylidene)oxalic aciddihydrazide, oxanilide, isophthalic acid dihydrazide, sebacic acidbis-phenylhydrazide, N,N′-diacetyladipic acid dihydrazide,N,N′-bis-salicyloyloxalic acid dihydrazide,N,N′-bis-salicyloylthiopropionic acid dihydrazide.

4. Phosphites and phosphonites, e.g. triphenyl phosphite, diphenylalkylphosphites, phenyl-dialkyl phosphites, tris(nonylphenyl)phosphite,trilauryl phosphite, trioctadecyl phosphite, distearyl-pentaerythritoldiphosphite, tris(2,4-di-tert-butylphenyl)phosphite,diisodecylpentaerythritol diphosphite,bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite,bis(2,4-di-cumylphenylypentaerythritol diphosphite,bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite,bis-isodecyloxy-pentaerythritol diphosphite,bis(2,4-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite,bis(2,4,6-tri-tert-butylphenyl)pentaerythritol diphosphite, tristearylsorbitol triphosphite,tetrakis(2,4-di-tert-butylphenyl)-4,4′-biphenylene diphosphonite,6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenzo[d,g]-1,3,2-dioxaphosphocine,bis(2,4-di-tert-butyl-6-methylphenyl)methylphosphite,bis(2,4-di-tert-butyl-6-methylphenyl) ethylphosphite,6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-dibenzo[d,g]-1,3,2-dioxaphosphocine,2,2′,2″-nitrilo[triethyl-tris(3,3′,5,5′-tetra-tert-butyl-1,1′-biphenyl-2,2′-diyl)-phosphite],2-ethylhexyl(3,3′,5,5′-tetra-tert-butyl-1,1′-biphenyl-2,2′-diyl)phosphite,5-butyl-5-ethyl-2-(2,4,6-tri-tert-butylphenoxy)-1,3,2-dioxaphosphirane.

5. Hydroxylamines, for example N,N-dibenzylhydroxylamine,N,N-diethylhydroxylamine, N,N-dioctylhydroxylamine,N,N-dilaurylhydroxylamine, N,N-ditetradecylhydroxylamine,N,N-dihexadecylhydroxylamine, N,N-dioctadecylhydroxylamine,N-hexadecyl-N-octadecylhydroxylamine,N-heptadecyl-N-octadecylhydroxylamine, N,N-dialkylhydroxylamine fromhydrogenated tallow fatty amines.

6. Nitrones, for example N-benzyl-alpha-phenylnitrone,N-ethyl-alpha-methylnitrone, N-octyl-alpha-heptylnitrone,N-lauryl-alpha-undecylnitrone, N-tetradecyl-alpha-tridecylnitrone,N-hexadecyl-alpha-pentadecylnitrone,N-octadecyl-alpha-heptadecylnitrone,N-hexadecyl-alpha-heptadecylnitrone,N-octadecyl-alpha-pentadecylnitrone,N-heptadecyl-alpha-heptadecylnitrone,N-octadecyl-alpha-hexadecylnitrone, nitrones derived fromN,N-dialkyl-hydroxylamines prepared from hydrogenated tallow fattyamines.

7. Thiosynergistic compounds, for example thiodipropionic acid dilaurylester or thiodipropionic acid distearyl ester.

8. Peroxide-destroying compounds, for example esters ofβ-thio-dipropionic acid, for example the lauryl, stearyl, myristyl ortridecyl ester, mercaptobenzimidazole, the zinc salt of2-mercaptobenzimidazole, zinc dibutyldithiocarbamate,dioctadecyldisulfide, pentaerythritoltetrakis(β-dodecylmercapto)propionate.

9. Polyamide stabilisers, for example copper salts in combination withiodides and/or phosphorus compounds and salts of divalent manganese.

10. Basic co-stabilisers, for example melamine, polyvinylpyrrolidone,dicyandiamide, triallyl cyanurate, urea derivatives, hydrazinederivatives, amines, polyamides, polyurethanes, alkali metal andalkaline earth metal salts of higher fatty acids, for example calciumstearate, zinc stearate, magnesium behenate, magnesium stearate, sodiumricinoleate, potassium palmitate, antimony pyrocatecholate or zincpyrocatecholate.

11. Nucleating agents, for example inorganic substances, e.g. talc,metal oxides, such as titanium dioxide or magnesium oxide, phosphates,carbonates or sulfates of preferably alkaline earth metals; organiccompounds, such as mono- or poly-carboxylic acids and their salts, e.g.4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodiumsuccinate or sodium benzoate; polymeric compounds, for example ioniccopolymerisates (“ionomers”). Special preference is given to1,3:2,4-bis(3′,4′-dimethylbenzylidene)sorbitol,1,3:2,4-di(paramethyldibenzylidene)sorbitol and1,3:2,4-di(benzylidene)sorbitol.

12. Additional fillers and reinforcing agents, for example calciumcarbonate, silicates, glass fibres, glass beads, talc, kaolin, mica,barium sulfate, metal oxides and hydroxides, carbon black, graphite,wood powders, and powders and fibres of other natural products,synthetic fibres.

13. Other additives, for example plasticisers, lubricants, emulsifiers,pigments, rheology additives, catalysts, flow improvers, opticalbrighteners, flame retardants, antistatics, blowing agents.

14. Benzofuranones and indolinones, for example as described in U.S.Pat. No. 4,325,863; U.S. Pat. No. 4,338,244; U.S. Pat. No. 5,175,312,U.S. Pat. No. 5,216,052; U.S. Pat. No. 5,252,643; DE-A-4 316 611; DE-A-4316 622; DE-A-4 316 876; EP-A-0 589 839 or EP-A-0 591 102, or3-[4-(2-acetoxyethoxy)phenyl]-5,7-di-tert-butyl-benzofuran-2-one,5,7-di-tert-butyl-3-[4-(2-stearoyl-oxyethoxy)phenyl]benzofuran-2-one,3,3′-bis[5,7-di-tert-butyl-3-(4-[2-hydroxyethoxy]phenyl)-benzofuran-2-one],5,7-di-tert-butyl-3-(4-ethoxyphenyl)benzofuran-2-one,3-(4-acetoxy-3,5-dimethylphenyl)-5,7-di-tert-butyl-benzofuran-2-one,3-(3,5-dimethyl-4-pivaloyloxy-phenyl)-5,7-di-tert-butyl-benzofuran-2-one,3-(3,4-dimethylphenyl)-5,7-di-tert-butyl-benzofuran-2-one,3-(2,3-dimethylphenyl)-5,7-di-tert-butyl-benzofuran-2-one or3-(2-acetyl-5-isooctylphenyl)-3-isooctylbenzofuran-2-one.

The costabilizers are added, for example, in concentrations of 0.01 to10%, relative to the total weight of the synthetic polymer to bestabilized.

Preferred further additives are phenolic antioxidants,light-stabilizers, processing stabilizers, solvents, pigments, dyes,plasticizers, compatibilizers, toughening agents, thixotropic agentsand/or metal deactivators.

In addition to the nano fillers other fillers may be used as reinforcingagents (item 12 in the list), for example talc, calcium carbonate,hydrotalcite, mica, kaolin, metal hydroxides, especially aluminiumhydroxide or magnesium hydroxide. These are added to the syntheticpolymers in concentrations, for example, of from 0.01 to 40%, based onthe overall weight of the synthetic polymers to be stabilized.

Carbon black as filler is added to the synthetic polymers inconcentrations, judiciously, of from 0.01 to 5%, based on the overallweight of the synthetic polymers to be stabilized.

Glass fibers as reinforcing agents are added to the synthetic polymersin concentrations, judiciously, of from 0.01 to 20%, based on theoverall weight of the synthetic polymers to be stabilized.

Further preferred compositions comprise in addition to components (a),(b) and (c) further additives as well, especially alkaline earth metalsalts of higher fatty acids, for example calcium stearate.

As a conventional stabilizer combination for processing syntheticpolymers, for example polyolefins, to form corresponding mouldings, thecombination of a phenolic antioxidant with a secondary antioxidant basedon an organic phosphite or phosphonite is recommended.

Incorporation of components (b) and (c) and, if desired, furtheradditives into the synthetic polymers is carried out by known methods,for example before or during moulding or else by applying the dissolvedor dispersed compounds to the synthetic polymer, if appropriate withsubsequent slow evaporation of the solvent.

The present invention also relates to a nanocomposite material in theform of a masterbatch or concentrate comprising component (a) in anamount of from 5 to 90%, component (b) in an amount of from 5 to 80%,and component (c) in an amount of from 1 to 50% by weight.

Components (b) and (c) and, if desired, further additives, can also beadded before or during polymerisation or before crosslinking.

Components (b) and (c), with or without further additives, can beincorporated in pure form or encapsulated in waxes, oils or polymersinto the synthetic polymer.

Components (b) and (c), with or without further additives, can also besprayed onto the synthetic polymer. It is able to dilute other additives(for example the conventional additives indicated above) or their meltsso that they too can be sprayed together with these additives onto thepolymer. Add ion by spraying on during the deactivation of thepolymerization catalysts is particularly advantageous, it being possibleto carry out spraying using, for example, the steam used fordeactivation.

In the case of spherically polymerized polyolefins it may, for example,be advantageous to apply components (b) and (c), with or without otheradditives, by spraying.

The synthetic polymers prepared in this way can be employed in a widevariety of forms, for example as foams, films, fibres, tapes, mouldingcompositions, as profiles or as binders for coating materials,especially powder coatings, adhesives, putties or especially asthick-layer polyolefin mouldings which are in long-term contact withextractive media, such as, for example, pipes for liquids or gases,films, fibres, geomembranes, tapes, profiles or tanks.

The preferred thick-layer polyolefin mouldings have a layer thickness offrom 1 to 50 mm, in particular from 1 to 30 mm, for example from 2 to 10mm.

The compositions according to the invention can be advantageously usedfor the preparation of various shaped articles. Examples are:

I-1) Floating devices, marine applications, pontoons, buoys, plasticlumber for decks, piers, boats, kayaks, oars, and beach reinforcements.

I-2) Automotive applications, in particular bumpers, dashboards,battery, rear and front linings, moldings parts under the hood, hatshelf, trunk linings, interior linings, air bag covers, electronicmoldings for fittings (lights), panes for dashboards, headlamp glass,instrument panel, exterior linings, upholstery, automotive lights, headlights, parking lights, rear lights, stop lights, interior and exteriortrims; door panels; gas tank; glazing front side; rear windows; seatbacking, exterior panels, wire insulation, profile extrusion forsealing, cladding, pillar covers, chassis parts, exhaust systems, fuelfilter/filler, fuel pumps, fuel tank, body side mouldings, convertibletops, exterior mirrors, exterior trim, fasteners/fixings, front endmodule, glass, hinges, lock systems, luggage/roof racks, pressed/stampedparts, seals, side impact protection, sound deadener/insulator andsunroof.

I-3) Road traffic devices, in particular sign postings, posts for roadmarking, car accessories, warning triangles, medical cases, helmets,tires.

I-4) Devices for plane, railway, motor car (car, motorbike) includingfurnishings.

I-5) Devices for space applications, in particular rockets andsatellites, e.g. reentry shields.

I-6) Devices for architecture and design, mining applications, acousticquietized systems, street refuges, and shelters.

II-1) Appliances, cases and coverings in general and electric/electronicdevices (personal computer, telephone, portable phone, printer,television-sets, audio and video devices), flower pots, satellite TVbowl, and panel devices.

II-2) Jacketing for other materials such as steel or textiles.

II-3) Devices for the electronic industry, in particular insulation forplugs, especially computer plugs, cases for electric and electronicparts, printed boards, and materials for electronic data storage such aschips, check cards or credit cards.

II-4) Electric appliances, in particular washing machines, tumblers,ovens (microwave oven), dish-washers, mixers, and irons.

II-5) Covers for lights (e.g. street-lights, lamp-shades).

II-6) Applications in wire and cable (semi-conductor, insulation andcable-jacketing).

II-7) Foils for condensers, refrigerators, heating devices, airconditioners, encapsulating of electronics, semi-conductors, coffeemachines, and vacuum cleaners.

III-1) Technical articles such as cogwheel (gear), slide fittings,spacers, screws, bolts, handles, and knobs.

III-2) Rotor blades, ventilators and windmill vanes, solar devices,swimming pools, swimming pool covers, pool liners, pond liners, closets,wardrobes, dividing walls, slat walls, folding walls, roofs, shutters(e.g. roller shutters), fittings, connections between pipes, sleeves,and conveyor belts.

III-3) Sanitary articles, in particular shower cubicles, lavatory seats,covers, and sinks.

III-4) Hygienic articles, in particular diapers (babies, adultincontinence), feminine hygiene articles, shower curtains, brushes,mats, tubs, mobile toilets, tooth brushes, and bed pans.

III-5) Pipes (cross-linked or not) for water, waste water and chemicals,pipes for wire and cable protection, pipes for gas, oil and sewage,guttering, down pipes, and drainage systems.

III-6) Profiles of any geometry (window panes) and siding.

III-7) Glass substitutes, in particular extruded plates, glazing forbuildings (monolithic, twin or multiwall), aircraft, schools, extrudedsheets, window film for architectural glazing, train, transportation,sanitary articles, and greenhouse.

III-8) Plates (walls, cutting board), extrusion-coating (photographicpaper, tetrapack and pipe coating), silos, wood substitute, plasticlumber, wood composites, walls, surfaces, furniture, decorative foil,floor coverings (interior and exterior applications), flooring, duckboards, and tiles.

III-9) Intake and outlet manifolds.

III-10) Cement-, concrete-, composite-applications and covers, sidingand cladding, hand rails, banisters, kitchen work tops, roofing, roofingsheets, tiles, and tarpaulins.

IV-1) Plates (walls and cutting board), trays, artificial grass,astroturf, artificial covering for stadium rings (athletics), artificialfloor for stadium rings (athletics), and tapes.

IV-2) Woven fabrics continuous and staple, fibers (carpets/hygienicarticles/geotextiles/monofilaments; filters; wipes/curtains(shades)/medical applications), bulk fibers (applications such asgown/protection clothes), nets, ropes, cables, strings, cords, threads,safety seat-belts, clothes, underwear, gloves; boots; rubber boots,intimate apparel, garments, swimwear, sportswear, umbrellas (parasol,sunshade), parachutes, paraglides, sails, “balloon-silk”, campingarticles, tents, airbeds, sun beds, bulk bags, and bags.

IV-3) Membranes, insulation, covers and seals for roofs, tunnels, dumps,ponds, dumps, walls roofing membranes, geomembranes, swimming pools,curtains (shades)/sun-shields, awnings, canopies, wallpaper, foodpacking and wrapping (flexible and solid), medical packaging (flexible &solid), airbags/safety belts, arm- and head rests, carpets, centreconsole, dashboard, cockpits, door, overhead console module, door trim,headliners, interior lighting, interior mirrors, parcel shelf, rearluggage cover, seats, steering column, steering wheel, textiles, andtrunk trim.

V) Films (packaging, dump, laminating, agriculture and horticulture,greenhouse, mulch, tunnel, silage), bale wrap, swimming pools, wastebags, wallpaper, stretch film, raffia, desalination film, batteries, andconnectors.

VI-1) Food packing and wrapping (flexible and solid), bottles.

VI-2) Storage systems such as boxes (crates), luggage, chest, householdboxes, pallets, shelves, tracks, screw boxes, packs, and cans.

VI-3) Cartridges, syringes, medical applications, containers for anytransportation, waste baskets and waste bins, waste bags, bins, dustbins, bin liners, wheely bins, container in general, tanks forwater/used water/chemistry/gas/oil/gasoline/diesel; tank liners, boxes,crates, battery cases, troughs, medical devices such as piston,ophthalmic applications, diagnostic devices, and packing forpharmaceuticals blister.

VII-1) Extrusion coating (photo paper, tetrapack, pipe coating),household articles of any kind (e.g. appliances, thermos bottle/clotheshanger), fastening systems such as plugs, wire and cable clamps,zippers, closures, locks, and snap-closures.

VII-2) Support devices, articles for the leisure time such as sports andfitness devices, gymnastics mats, ski-boots, inline-skates, skis, bigfoot, athletic surfaces (e.g. tennis grounds); screw tops, tops andstoppers for bottles, and cans.

VII-3) Furniture in general, foamed articles (cushions, impactabsorbers), foams, sponges, dish clothes, mats, garden chairs, stadiumseats, tables, couches, toys, building kits (boards/figures/balls),playhouses, slides, and play vehicles.

VII-4) Materials for optical and magnetic data storage.

VII-5) Kitchen ware (eating, drinking, cooking, storing).

VII-6) Boxes for CD's, cassettes and video tapes; DVD electronicarticles, office supplies of any kind (ball-point pens, stamps andink-pads, mouse, shelves, tracks), bottles of any volume and content(drinks, detergents, cosmetics including perfumes), and adhesive tapes.

VII-7) Footwear (shoes/shoe-soles), insoles, spats, adhesives,structural adhesives, food boxes (fruit, vegetables, meat, fish),synthetic paper, labels for bottles, couches, artificial joints (human),printing plates (flexographic), printed circuit boards, and displaytechnologies.

VII-8) Devices of filled polymers (talc, chalk, china clay (kaolin),wollastonite, pigments, carbon black, TiO₂, mica, nanocomposites,dolomite, silicates, glass, asbestos).

Thus, a further embodiment of the present invention relates to a shapedarticle, in particular a film, pipe, profile, bottle, tank or container,fiber containing a composition as described above.

A further embodiment of the present invention relates to a moldedarticle containing a composition as described above. The molding is inparticular effected by injection, blow, compression, roto-molding orslush-molding or extrusion.

The present invention also relates to a process for the preparation of asynthetic polymer nanocomposite material which comprises melt mixing amixture of a) a synthetic polymer, b) a filler, and c) as dispersingagent a polymer which is based on a long chain alkyl meth(acrylate).

The melt mixing can be carried out in any heatable container equippedwith a stirrer, for example in a closed apparatus such as a kneader,mixer or stirred vessel. The incorporation is preferably carried out inan extruder or in a kneader. It is immaterial whether processing takesplace in an inert atmosphere or in the presence of oxygen.

The addition of components (a), (b) and (c) can be carried out in allcustomary mixing machines in which the polymer is melted and mixed withthe additives. Suitable machines are known to those skilled in the art.They are predominantly mixers, kneaders and extruders.

The process is preferably carried out in an extruder by introducing theadditive during processing. Particularly preferred processing machinesare single-screw extruders, contrarotating and corotating twin-screwextruders, planetary-gear extruders, ring extruders or co-kneaders. Itis also possible to use processing machines provided with at least onegas removal compartment to which a vacuum can be applied. Suitableextruders and kneaders are described, for example, in Handbuch derKunststoffextrusion, Vol. 1, Grundlagen, Editors F. Hensen, W. Knappe,H. Potente, 1989, pp. 3-7, ISBN:3-446-143394; and Vol. 2Extrusionsanlagen 1986, ISBN 3-446-14329-7. For example, the screwlength is 1-60 screw diameters, preferably 35-48 screw diameters. Therotational speed of the screw is preferably 10 to 600 rotations perminute (rpm), for example 25-300 rpm. The maximum throughput isdependent on the screw diameter, the rotational speed and the drivingforce. The process of the present invention can also be carried out at alevel lower than maximum throughput by varying the parameters mentionedor employing weighing machines delivering dosage amounts. If a pluralityof components are added, these can be premixed or added individually.

Also of interest is a process for the preparation of a synthetic polymernanocomposite material, wherein the melt mixing of the components(synthetic polymer, filler and dispersing agent prepared by controlledfree radical polymerization) occurs between 120 and 290° C., preferablybetween 140 and 250° C., for example between 170 and 230° C.

The present invention also relates to synthetic polymer nanocompositesobtained by the above mentioned process.

The preferred components (b) and (c), and optionally further additives,in the process for the preparation of a synthetic polymer nanocompositematerial are the same as those described for the composition.

A preferred embodiment of the present invention is also the use of apolymer based on a long chain alkyl meth(acrylate) to intercalate andexfoliate a filler and disperse the filler in a synthetic polymer matrixto form a nanocomposite material.

The preferred dispersing agent, filler and synthetic polymer, andoptionally further additives, for this use are the same as thosedescribed for the composition.

The following examples illustrate the invention further. Parts orpercentages relate to weight.

Gel permeation chromatography (GPC) is performed on a Waters Associatesliquid chromatograph equipped with differential refractometer and a setof four 600 mm×7.56 mm columns comprising three PLgel 5μ mixed C columnsand one PLgel 3μ mixed E column (Polymer Laboratories). Tetrahydrofuran(flow rate of 1.0 mL/min) is used as eluent at 22±2° C. The columns arecalibrated with narrow polydispersity polystyrene standards (PolymerLaboratories) and GPC molecular weights are given as polystyreneequivalents.

EXAMPLE 1 Preparation of Acrylic Random Copolymers by ConventionalRadical Polymerization (Conv)

a) Preparation of poly((octadecyl acrylate)-co-(dimethylaminoethylacrylate)) (PODA-co-DMAEA).

A solution of 300 g (924.4 mmol) of octadecyl acrylate, 33.3 g (232.8mmol) of 2-(N,N-dimethylamino)ethyl acrylate and 10.95 g (66.7 mmol) ofAIBN (azaisobutyronitrile) in 400 ml of dry toluene is degassed bypurging argon for 3 hours. Polymerization is carried out at 60° C. withstirring under argon for 67.5 hours. The reaction solution isprecipitated into vigorously stirred acetone (2.5 L). The polymer iscollected by filtration and vacuum-dried for two days (light yellowsolid; ¹H NMR: conversion 100%; GPC: M_(n) 22990, M_(w)/M_(n) 3.7).

b) Preparation of poly((octadecyl acrylate)-co-(maleic anhydride))(PODA-co-MAH).

A solution (A) of stearyl acrylate (ODA, 300.0 g, 0.924 mol), maleicanhydride (MAH, 45 g, 0.46 mol) and AIBN (2.7 g. 16.5 mmol) in 930 mL ofdry THF and a solution (B) of stearyl acrylate (150 g, 0.46 mol) andAIBN (1.35 g, 8.26 mmol) in 320 mL of dry THF are degassed by purgingwith argon, combined with vacuum. Solution A is heated and stirred at70° C. under argon for 2 hours, then, solution B is transferred tosolution A by cannula. After the addition, the mixture is heated andstirred at same temperature for a total time of 24 hours. The polymersolution is precipitated into acetone (6 L) and the resultant polymer iscollected by filtration and dried in a vacuum oven for two days. (whitesolid; ¹HNMR: conversion 96.3% for ODA and 100% for MAH; GPC: M_(n)4200, M_(w)/M_(n) 1.49).

c) Preparation of poly((octadecyl acrylate)-co-(N-vinylpyrrolidone))(PODA-co-NVP).

A solution (A) of stearyl acrylate (ODA, 50.0 g, 0.154 mol), N-vinylpyrrolidone (NVP, 4.28 g, 0.0385 mol) and AIBN (1.78 g, 10.8 mmol) indry toluene (400 mL) and a solution (B) of stearyl acrylate (450 g,1.387 mol), N-vinyl pyrrolidone (38.5 g, 0.347 mol) and AIBN (16.04 g.97.69 mmol) in dry toluene (600 mL) are degassed by purging with argon,combined with vacuum. Solution A is first heated and stirred at 100° C.under argon for 40 minutes, then aliquots (171, 233, 317 mL andremainder of solution) are added by syringe at 40 minute intervals.After addition, the mixture is heated and stirred at same temperaturefor further 40 minutes. The total polymerization time is 4.5 hours. Thepolymer solution is precipitated into acetone (6 L) and the resultantpolymer is collected by filtration and dried in a vacuum oven for threedays. (white solid; ¹H NMR: conversion 99% for ODA and 100% for NVP;GPC: M_(n) 9300, M_(w)/M_(n) 1.47).

d) Preparation of poly((octadecyl methacrylate)-co-(N-vinylpyrrolidone))(PODMA-co-NVP).

A solution of 404 g (1190 mmol) of octadecyl methacrylate, 33.2 g (298mmol) of N-vinyl pyrrolidone, 7.9 g (87.4 mmol) of 1-butanethiol and1.44 g (8.74 mmol) of AIBN (azaisobutyronitrile) in 1000 ml of drytoluene is degassed by purging with argon for 3 hours. Polymerization iscarried out at 60° C. with stirring under argon for 63.0 hours. Theresultant solution is precipitated into vigorously stirred acetone (5.0L). The polymer is collected by filtration and vacuum-dried for two days(white solid, ¹H NMR: conversion 100% for ODMA and 48% for NVP; GPC:M_(n) 6000, M_(w)/M_(n) 1.48).

e) Preparation of poly((octadecyl acrylate)-co-(N-vinylpyrrolidone))(PODA-co-NVP).

A solution (A) of octadecyl acrylate (ODA, 500 g, 1.54 mol), N-vinylpyrrolidone (NVP, 42.8 g, 0.385 mol) and AIBN (0.87 g. 5.3 mmol) in 1000mL of dry toluene (solution A) and a solution (B) of AIBN (17 g. 103.3mmol) in 260 mL of dry toluene are degassed by purging with argon,combined with vacuum. Solution A is first heated and stirred at 110° C.under argon for 20 minutes, then, solution B is added by syringe in 20ml aliquots at 5 minute intervals. When the addition is complete, themixture is heated and stirred at same temperature for a further 14hours. The total polymerization time is 15.5 hours. The polymer solutionis precipitated into acetone (6 L) and the resultant polymer is filteredand dried in a vacuum oven for three days. (white solid; ¹H NMR:conversion 100% for both ODA and NVP; GPC: M_(n) 24900, M_(w)/M_(n)5.07).

TABLE 1 Polymers prepared by conventional radical polymerizationPolymer¹⁾ Prepared by²⁾ DP(1)³⁾ DP(2)³⁾ M_(n) ⁴⁾ M_(w)/M_(n) ⁵⁾ 1a)PODA-co-MAH Conv 4.0 1.0 7030 (4100) — 1b) PODA-co-PEGMEA Conv 14.7 4.97400 (6100) 1.2 1c) PODA-co-DMAEA Conv 4.0 1.0 (23000) 3.7 1d)PODA-co-BA-co-DMAEA Conv 2.0/6.0 2.0 (8800) 10.8 1e) PODA-co-BA-co-MAHConv 2.0/6.0 2.0 (4550) 3.1 1f) PODA-co-DEGEEA Conv 4.0 1.0 insol.insol. 1g) PODA-co-PEGMEA Conv 4.0 1.0 (4300) 1.7 1h) PODA-co-MAH Conv3.0 1.0 (5200) 2.32 1i) PODA-co-MAH Conv 5.0 1.0 (6100) 2.70 1j)PODA-co-MAH Conv1 3.0 1.0 (4200) 1.49 1k) PODA-co-NVP Conv5 4.0 1.0 NANA 1l) PODA-co-NVP Conv4 4.0 1.0 (24900) 5.07 1m) PODMA-co-NVP Conv3 4.01.0 (6000) 1.48 1n) PODA-co-NVP Conv3 4.0 1.0 (49800) 3.84 1o)PODMA-co-MAH Conv3 3.0 1.0 (5100) 1.55 1p) PODA-co-NVP Conv2 4.0 1.0(9300) 1.47 1q) PODA-co-GA Conv 4.0 1.0 (48300) 5.08 1r) PODMA-co-NVPConv3 4.0 1.0 (18700) 1.73 ¹⁾Abbreviations: PODA-co-MAH ispoly(octadecyl acrylate)-co-(maleic anhydride), PODA-co-PEGMEA ispoly(octadecyl acrylate)-co-(poly(ethylene glycol) methyl etheracrylate), PODA-co-DMAEA is poly(octadecylacrylate)-co-(2-dimethylaminoethyl acrylate), PODA-co-BA-co-DMAEA ispoly(octadecyl acrylate)-co-(butyl acrylate)-(2-dimethylaminoethylacrylate), PODA-co-BA-co-MAH is poly(octadecyl acrylate)-co-(butylacrylate)-co-(maleic anhydride), PODA-co-DEGEEA is poly(octadecylacrylate)-co-(diethylene glycol ethyl ether acrylate), PODA-co-NVP ispoly(octadecyl acrylate)-co-(N-vinylpyrrolidone), PODMA-co-NVP ispoly(octadecyl methacrylate)-co-(N-vinylpyrrolidone), PODMA-co-MAH ispoly(octadecyl methacrylate)-co-(maleic anhydride), PODA-co-GA ispoly(octadecyl acrylate)-co-(glycidyl acrylate), ²⁾Method of synthesis:Conv Conventional radical polymerization with AIBN initiator asdisclosed for example in Example 1a. Conv1 Conventional radicalpolymerization with AIBN initiator and portionwise addition of monomersas disclosed for example in Example 1b. Conv2 Conventional radicalpolymerization with AIBN initiator and portionwise addition of monomersas disclosed for example in Example 1c. Conv3 Conventional radicalpolymerization with AIBN initiator and butanethiol transfer agent asdisclosed for example in Example 1d. Conv4 Conventional radicalpolymerization with AIBN initiator as disclosed for example in Example1e. Conv5 Conventional radical polymerization with AIBN initiator asdisclosed for example in Example 1a but with a reaction temperature of70° C. ³⁾DP1 and DP2 indicate the overall composition and representaverage ratio of the comonomers in the polymer chain. ⁴⁾Molecular weightobtained from ¹H NMR integration, the values in parentheses are fromGPC. ⁵⁾Polydispersity of polymer obtained from GPC.

EXAMPLE 2 Preparation of Acrylic Statistical Copolymers by RAFTPolymerization (RAFT)

Preparation of poly((octadecyl acrylate)-co-(dimethylaminoethylacrylate) PODA-co-DMAEA.

A solution of 200 g (616 mmol) of octadecyl acrylate, 22.1 g (154 mmol)of 2-(N,N-dimethylamino)ethyl acrylate, 12.0 g (44.4 mmol) of butyl1-phenylethyl trithiocarbonate and 729 mg (4.44 mmol) of AIBN in 300 mLof dry toluene is degassed by purging argon for 3 hours. Polymerizationis carried out at 60° C. with stirring under argon for 24 hours. Thereaction solution was precipitated into vigorously stirred acetone (2.5L). The polymer is collected by filtration and vacuum-dried for two days(yellow solid; ¹H NMR: conversion 95.1%; GPC: M_(n) 5590, M_(w)/M_(n)1.1).

TABLE 2 Copolymers prepared by RAFT polymerization Polymer¹⁾ Preparedby²⁾ DP(1)³⁾ DP(2)³⁾ M_(n) ⁴⁾ M_(w)/M_(n) ⁵⁾ 2a) PODA-co-DMAEA RAFT 30.07.0 11000 (13700) 1.2 2b) PODA-co-PEGMEA RAFT 26.1 6.6 11500 (8800)  1.22c) PODA-co-NVP RAFT 53.1 14.2 19250 (16200) 1.23 2d) PODA-co-DMAEA RAFT12.3 3.1 4700 (5600) 1.08 2e) PODA-co-MAH RAFT3 4.4 13.6 15000 (6300) 1.29 2f) PODA-co-MMA-co-MAH RAFT3 11.0/2.0 2.0 4300 (5300) 1.13 2g)PODA-co-DEGEEA RAFT3 12.5 1.4 4700 (5900) 1.06 2h) PODA-co-DMAEA RAFT312.5 1.4 4600 (5800) 1.07 2i) PODA-co-DMAEA RAFT3 96.7 10.8 33500(34900) 1.14 2j) PODA-co-MAH RAFT3 38.5 9.0 13800 (10400) 1.28 2k)PODA-co-MAH RAFT3 50 7.0 17300 (7200)  1.27 2l) PODA-co-MAH RAFT3 45.52.3 15400 (8000)  1.32 2m) PODA-co-MEP RAFT3 43.6 1.53 14900 (8400) 1.41 2n) PLA-co-MAH RAFT3 69.0 21.0 18900 (4000)  1.62 2o) PODA-co-GMARAFT3 54.8 15.1 20300 (15600) 1.29 2p) PODA-co-MAA RAFT3 10.0 1.0(14500) 1.21 2q) PODA-co-MAA RAFT3 5.0 1.0 (13900) 1.21 2r)PODA-co-MA-co-MAA RAFT3 9.0/1.0 1.0 (14900) 1.21 2s) PODA-co-MAH-co-AARAFT3 9.0 1.0/1.0 (12800) 1.18 ¹⁾Abbreviations: PODA-co-DMAEA ispoly(octadecyl acrylate)-co-(2-dimethylaminoethyl acrylate),PODA-co-PEGMEA is poly(octadecyl acrylate)-co-(poly(ethylene glycol)methyl ether acrylate), PODA-co-NVP is poly(octadecylacrylate)-co-(N-vinylpyrrolidone), PODA-co-MAH is poly(octadecylacrylate)-co-(maleic anhydride), PODA-co-MMA-co-MAH is poly(octadecylacrylate)-co-(methyl methacrylate)-co-(maleic anhydride), PODA-co-DEGEEAis poly(octadecyl acrylate)-co-(diethylene glycol ethyl ether acrylate),PODA-co-MEP is poly(octadecyl acrylate)-co-(methacrylolyoxyethylphosphate), PLA-co-MAH is poly(lauryl acrylate)-co-(maleic anhydride),PODA-co-GMA is poly(octadecyl acrylate)-co-(glycidyl methacrylate),PODA-co-MAA is poly(octadecyl acrylate)-co-(methacrylic acid), acid),PODA-co-PMA-co-MAA is poly(octadecyl acrylate)-co-(methylacrylate)-co-(methacrylic acid) PODA-co-MAH-co-AA is poly(octadecylacrylate)-co-poly(maleic anhydride)-co-(acrylic acid) ²⁾Method ofsynthesis: RAFT Polymerization with reversible addition fragmentationchain transfer as disclosed for example in Example 2 (random copolymer)or 4 (block copolymer). RAFT3 Polymerization with reversible additionfragmentation chain transfer as disclosed for example in Example 4 butwith S-dodecyl S-(1-phenylethyl) trithiocarbonate as RAFT agent. ³⁾DP1and DP2 indicate the overall composition and represent average ratio ofthe comonomers in the polymer chain. ⁴⁾Molecular weight obtained from ¹HNMR integration, the values in parentheses are from GPC.⁵⁾Polydispersity of polymer obtained from GPC.

EXAMPLE 3 Preparation of Acrylic Block Copolymers by Nitroxide MediatedPolymerization (NMP). The Preparation of the Compound of the FormulaNMP-1

is disclosed in Example 1 of GB-A-2 361 235.a) Preparation of poly(octadecyl acrylate) (PODA).

A mixture of 103.1 g (317.7 mmol) of octadecyl acrylate and 5.55 g (15.4mmol) of the compound of the formula NMP-1 [preparation disclosed inExample 1 of GB-A-2 361 235] is de-gassed by three freeze-evacuate-thawcycles. The mixture is heated in an oil bath with stirring at 120° C.under argon for 48 hours. The polymer is diluted with 60 ml of tolueneand precipitated into ethanol (800 mL at 35° C.), filtered, washed withethanol and dried at room temperature in a vacuum oven for 48 hours(white solid; ¹HNMR: conversion 74.6%, M_(n) 4800; GPC: M_(n) 6310M_(w)/M_(n) 1.2).

b) Preparation of poly(octadecylacrylate)-block-poly(2-(N,N-dimethylamino)ethyl acrylate).(PODA-b-PDMAEA)

A solution of 15 g (3.14 mmol) of poly(octadecyl acrylate) [preparedaccording to Example 3a] and 7 g (48.8 mmol) of2-(N,N-dimethylamino)ethyl acrylate in dry toluene (25 mL) in a bulbampoule is degassed by freeze-thaw method. The sealed ampoule is placedin an oil bath at 120° C. for 42.5 hours. The polymer is precipitatedinto vigourously stirred methanol (400 mL). The solid is filtered,washed with methanol and dried at 35° C. in a vacuum oven overnight(white solid; ¹H NMR: conversion 41.2%, M_(n) 5700; GPC: M_(n) 7200M_(w)/M_(n) 1.2).

TABLE 3 PODA and block copolymers prepared by nitroxide mediatedpolymerization Prepared M_(w)/ Polymer¹⁾ by²⁾ DP(1)³⁾ DP(2)⁴⁾ M_(n) ⁵⁾M_(n) ⁶⁾ 3a) PODA NMP 12.3 4400 (4800) 1.3 3b) PODA-b-PVP NMP 15.6 6.26100 — 3c) PODA-b- NMP 15.6 5.6 7960 — PEGMEA 3d) PODA-b-HEA NMP 19.58.3 7700 1.3 3e) PODA-b- NMP 13.6 6.4 5700 (7200) 1.2 DMAEA 3f)PODA-b-HEA NMP 19.5 8.3 7700 1.3 3g) PODA-b-AN NMP 17.1 21.0 7700 — 3h)PODA-b-VP NMP 15.6 6.2 6100 — 3i) PODA-b-DMA NMP 20.0 7.7 7600 —¹⁾Abbreviations: PODA is poly(octadecyl acrylate), PODA-b-VP ispoly(octadecyl acrylate)-block-poly(N-vinylpyridine), PODA-b-PEGMEA ispoly(octadecyl acrylate)-block-poly(poly(ethylene glycol) methyl etheracrylate), PODA-b-HEA is poly(octadecylacrylate)-block-poly(2-hydroxyethyl acrylate), PODA-b-DMAEA ispoly(octadecyl acrylate)-block-poly(2-dimethylaminoethyl acrylate),PODA-b-AN is poly(octadecyl acrylate)-block-poly(acrylonitrile),PODA-b-DMA is poly(octadecylacrylate)-block-poly(N,N-dimethylacrylamide), ²⁾Method of synthesis: NMPis nitroxide mediated polymerization as disclosed for example in Example3. ³⁾Degree of polymerization of first block. ⁴⁾Degree of polymerizationof second block. ⁵⁾Molecular weight obtained from ¹H NMR integration,the values in parentheses are from GPC. ⁶⁾Polydispersity of polymerobtained from GPC.

EXAMPLE 4 Preparation of Acrylic Block Copolymers by RAFT

a) Preparation of poly(octadecyl acrylate) (PODA).

A solution of 200 g (616 mmol) of octadecyl acrylate, 12.0 g (44.4 mmol)of S-butyl S′-phenylethyl trithiocarbonate and 729 mg (4.44 mmol) ofAIBN in 250 ml of dry toluene is de-gassed by purging Argon for 3 hours.Polymerization is carried out at 60° C. for 20 hours with stirring underargon (¹HNMR: conversion 94.4%; GPC: Mn 5170, Mw/Mn 1.1).

b) Preparation of poly(octadecyl acrylate)-block-poly(dimethylaminoethylacrylate) (PODA-b-DMAEA).

A solution of 22.1 g (154 mmol) of 2-(N,N-dimethylamino)ethyl acrylateand 364 mg (2.22 mmol) of AIBN in 50 ml of dry toluene is degassed bypurging Argon for 3 hours. This solution is added to above solution[Example 4a] by syringe. The mixture is stirred at 60° C. under argonfor 22 hours. The reaction mixture is precipitated into vigorouslystirred acetone (2.5 L). The polymer is collected by filtration andvacuum-dried for two days. (yellow solid; ¹HNMR: total conversion 97.5%;GPC: Mn 5400, Mw/Mn 1.1).

TABLE 4 PODA and block copolymers prepared by RAFT polymerisationPolymer¹⁾ Prepared by²⁾ DP(1)³⁾ DP(2)⁴⁾ M_(n) ⁵⁾ M_(w)/M_(n) ⁶⁾ 4a) PODARAFT 14.8 —  5200 — 4b) PODA-b-NVP RAFT2 21.6 2.9  7700 — 4c)PODA-b-DMAEA 5000 RAFT 14.8 3.7 5600 (5400) 1.09 4d) PODA-b-DMAEA 15000RAFT 41.7 8.5 14800 (15600) 1.21 4e) PODA-b-(PMMA-co-MAH)⁷⁾ RAFT36.0/1.0 1.0  (5800) 1.14 4f) PODA-b-DMAEA⁷⁾ RAFT3 10.0 1.0 4200 (5900)1.08 4g) PODA-b-(PMA-co-MAA)⁷⁾ RAFT3 9.0 1.0/1.0 (13500) 1.21 4h)PODA-b-(PMAH-co-AA)⁷⁾ RAFT3 9.0 1.0/1.0 (12500) 1.28 ¹⁾Abbreviations:PODA-b-NVP is poly(octadecyl acrylate)-block-poly(N-vinylpyrrolidone),PODA-b-DMAEA is poly(octadecyl acrylate)-block-poly(2-dimethylaminoethylacrylate), PODA-b-(PMMA-co-MAH) is poly(octadecylacrylate)-block-poly(methyl methacrylate)-co-(mmaelic anhydride),PODA-b-(PMA-co-MAA) is poly(octadecyl acrylate)-block-poly(methylacrylate)-co-(methacrylic acid), PODA-b-(PMAH-co-AA) is poly(octadecylacrylate)-block-poly(maleic anhydride)-co-(acrylic acid), ²⁾Method ofsynthesis: RAFT Polymerization with reversible addition fragmentationchain transfer as disclosed for example in Example 2 (random copolymer)or 4 (block copolymer). RAFT2 Polymerization with reversible additionfragmentation chain transfer as disclosed for example in Example 4 butwith O-pentafluorophenyl S-benzyl xanthate as RAFT agent. RAFT3Polymerization with reversible addition fragmentation chain transfer asdisclosed for example in Example 4 but with S-dodecyl S-(1-phenylethyl)trithiocarbonate as RAFT agent. ³⁾Degree of polymerization of firstblock. ⁴⁾Degree of polymerization of second block. ⁵⁾Molecular weightobtained from ¹H NMR integration, the values in parentheses are fromGPC. ⁶⁾Polydispersity of polymer obtained from GPC. ⁷⁾In case of astatistical or gradient copolymer block the two numbers indicate theoverall degrees of polymerization and represent average ratio of thecomonomers in the polymer chain.

EXAMPLE 5 Preparation of Acrylic Block Copolymers Using a Macroinitiator

a) Preparation of poly((ethylene glycol)methylether)-block-poly(octadecyl acrylate).

A solution of 6.29 g (3.78 mmol) of an azo-macroinitiator [preparedaccording to a procedure of Rentsch and Schultz, Makromol. Chem. 1977,178, 2535 with polyethylene glycol mono-methyl ether MW 750] and 21.14 g(65.1 mmol) of octadecyl acrylate in 15 ml of dry toluene in an ampouleis degassed by three freeze-pump-thaw cycles. The sealed ampoule isplaced in an oil bath at 120° C. for 2 hours. The polymer solution isprecipitated into 300 ml of methanol. The solid is collected byfiltration, washed twice with methanol (20 ml) and dried in vacuum ovenfor two days. The yield of the polymer is 22.4 g (76%). GPC Mn 8900;Mw/Mn 5.9.

TABLE 5 Block copolymers prepared using macroinitiator Prepared M_(w)/Polymer¹⁾ by²⁾ DP(1)³⁾ DP(2)⁴⁾ M_(n) ⁵⁾ M_(n) ⁶⁾ 5a) PODA-b- macroinit16.0 26.4  9400 (8900) 5.9 PEO750 5b) PODA-b- macroinit 22.0 38.2 13500(6500) 1.9 PEO1000 ¹⁾Abbreviations: PODA-b-PEO750 is poly(octadecylacrylate)-block-poly(ethylene glycol) (PEG MW 750), PODA-b-PEO1000 ispoly(octadecyl acrylate)-block-poly(ethylene glycol) (PEG MW 1000),²⁾Method of synthesis: Macroinit is conventional polymerization withmacroinitiator as disclosed for example in Example 5. ³⁾Degree ofpolymerization of first block. ⁴⁾Degree of polymerization of secondblock. ⁵⁾Molecular weight obtained from ¹H NMR integration, the valuesin parentheses are from GPC. ⁶⁾Polydispersity of polymer obtained fromGPC.

EXAMPLE 6 Preparation of poly(octadecylacrylate)-block-poly(4-vinylbenzyltriethylammonium chloride)(PODA-b-VBTEAC)

A solution of 2.0 g (3.28 mmol VBC) of P(ODA-bl-VBC) and 1.77 g (17.4mmol) of triethylamine in 10 ml of toluene is stirred at 90° C. for 48hours. The solvent and unreacted triethylamine are removed under vacuum.The extent of quaternization from NMR is 71.86%. ¹H NMR (CDCl₃): δ4.0(OCH₂ from ODA unit), δ3.4 (NCH₂ from 4-vinylbenzyltriethylammoniumchloride unit).

TABLE 6 Copolymers prepared by RAFT or NMP polymerization andquaternized Polymer¹⁾ Prepared by²⁾ DP(1)³⁾ DP(2)⁴⁾ M_(n) ⁵⁾ M_(w)/M_(n)⁶⁾ 6a) PODA-b-VBTEAC NMP Q 19.5 10.5 10000  — 6b) PODA-b-VBTBPC NMP Q19.5 14.6 — — 6c) PODA-b-VBDHEA NMP Q 19.5 8.4 9800 — 6d)PODA-co-AETMAI⁷⁾ RAFT3 Q 15.5 3.8 6000 (6300) 1.06 6e) PODA-co-AEBDMAB⁷⁾RAFT3 Q 13.4 3.4 5200 (6300) 1.09 6f) PODA-co-AEDMAC⁷⁾ RAFT3 Q 14.5 3.65600 (6500) 1.13 6g) PODA-b-AEBDMAB RAFT3 Q 12.9 3.2 5200 (5100) 1.066h) PODA-b-AETMAI RAFT3 Q 14.7 2.2 5800 (5100) 1.06 6i)PODA-co-AEBDMAB⁷⁾ RAFT3 Q 12.5 1.4 (5700) 1.06 6j) PODA-b-AEBDMAB RAFT3Q 11.4 1.3 4500 (5700) 1.07 6k) PODA-co-AEBDMAB⁷⁾ RAFT3 Q 98.5 10.935500 (8700)  1.37 ¹⁾Abbreviations: PODA-b-VBTEAC is poly(octadecylacrylate)-block-poly(4-vinylbenzyltriethylammonium chloride),PODA-b-VBTBPC is poly(octadecylacrylate)-block-poly(4-vinylbenzyltributylphosphonium chloride),PODA-b-VBDHEA is poly(octadecylacrylate)-block-poly(4-vinylbenzydi(hydroxyethyl)ammonium chloride),PODA-co-AETMAI is poly(octadecyl acrylate)-co-(acryloyloxyethyltrimethyl ammonium iodide), PODA-co-AEBDMAB is poly(octadecylacrylate)-co-(acryloyloxyethyl butyl dimethyl ammonium bromide),PODA-co-AEDMAC is poly(octadecyl acrylate)-co-(acryloyloxyethyl dimethylammonium chloride), PODA-b-AEBDMAB is poly(octadecylacrylate)-block-poly(acryloyloxyethyl butyl dimethyl ammonium bromide),PODA-b-AETMAI is poly(octadecyl acrylate)-block-poly(acryloyloxyethyltrimethyl ammonium iodide), ²⁾Method of synthesis: Copolymers wereprepred by one of the following routes NMP is nitroxide mediatedpolymerization as disclosed for example in Example 3. RAFT3 ispolymerization with reversible addition fragmentation chain transfer asdisclosed for example in Example 4 but with S-dodecyl S-(1-phenylethyl)trithiocarbonate as RAFT agent and then quaternized as disclosed forexample in Example 6. ³⁾Degree of polymerization of first block.⁴⁾Degree of polymerization of second block. ⁵⁾Molecular weight obtainedfrom ¹H NMR integration, the values in parentheses are from GPC.⁶⁾Polydispersity of polymer obtained from GPC. ⁷⁾In case of statisticalor gradient copolymers DP1 and DP2 indicate the overall composition andrepresent average ratio of the comonomers in the polymer chain.

EXAMPLE 7 Preparation of Polypropylene Nanocomposites in a Batch MixerBased on Unmodified Sodium Montmorillonite

50 g of polypropylene [Basell KY 6100®], is blended with 0.25% ofIrganox 1010® (pentaerythritoltetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]) and 0.25% ofIrgafos 168® (tris(2,4-di-tert-butylphenyl) phosphite), 5% of amontmorillonite day [Cloisite (Na⁺)® obtained from Southern ClayIndustries] and 2.5% of a dispersing agent according to Table 7 in aplastic cup and then added to a batch mixer operating at 25 rpm and 180°C., the mixture is then taken to 50 rpm for 10 minutes. Small scaleinjection moulding is performed with a CS-183 MMX Minimax moulder. Themixing chamber is pre-heated to 230° C. and the mould is oven heated to120° C. for one hour prior to injection moulding. Approximately 5 g ofthe material is placed in the mixing chamber and heated for 4 to 5minutes. A small shot is taken from the CS-183 MMX Minimax moulder priorto placing the mould in position. Six tensile bars with the dimensions18 mm by 5 mm by 0.85 mm are produced for each of the 5 g material.

Tensile testing is performed according to ASTM D 638 with a Rheometricsmini material tensile tester [Minimat 2000®] equipped with a 1000 N loadcell (40 mm/min). The results are summarized in Table 7.

TABLE 7 Normalized d-001 Modulus of Elongation at Example Dispersingagent (Å)^(c)) Elasticity^(d)) break (%)^(e)) 7a^(a)) none 10 1.12 0.977b^(b)) PODA (3a) 12 1.20 1.12 7c^(b)) PODA-b-VP (3b) 12 1.24 1.157d^(b)) PODA-b-PEGMEA (3c) 17 1.18 1.22 7e^(b)) PODA-b-HEA (3d) 12 1.230.82 ^(a))Comparative Example. ^(b))Example according to the invention(number in parentheses). ^(c))Interlayer distance determined by X-raydiffraction. ^(d))Normalized modulus of elasticity relative topolypropylene processed under similar conditions (=1.0). ^(e))Normalizedelongation at break relative to polypropylene processed under similarconditions (=1.0).

The X-ray diffraction (XRD) spectra show that all acrylic copolymersaccording to Table 7 intercalate the used day in the direct meltblending experiments in the batch mixer. This is demonstrated by anincrease in d-spacing of from 10 Å (comparative Example 7a) to 17 Å(Example 7d according to the invention). The elasticity modulus ofsamples is enhanced by 18-24% with respect to polypropylene withoutdispersing agent. Surprisingly, the elongation at break is also enhancedby 12-30% (except PODA-b-PHEA).

EXAMPLE 8 Preparation of Polypropylene Nanocomposites in a Batch MixerBased on Unmodified Sodium Montmorillonite

The polypropylene nanocomposites are prepared in analogy to Example 7with the polypropylene Basell HP400N® instead of Basell KY 6100®. Theresults are summarized in Table 8.

TABLE 8 Normalized Modulus of Example Dispersing agent Elasticity^(d))8a^(a)) none 1.20 8b^(b)) PODA-b-DMAEA (3e) 1.39 8c^(b)) PODA-co-EGMEA(1b) 1.36 8d^(b)) PODA-co-MAH (1a) 1.32 8e^(b)) PODA-co-DMAEA (1c) 1.228f^(b)) PODA-co-DMAEA (2a) 1.33 8g^(b)) PODA-co-BA-co-DMAEA (1d) 1.278h^(b)) PODA-co-BA-co-MAH (1e) 1.26 8i^(b)) PODA-co-DEGEEA (1f) 1.378j^(b)) PODA-co-EGMEA (1g) 1.33 8k^(b)) PODA-co-EGMEA (2b) 1.47^(a))Comparative Example. ^(b))Example according to the invention(number in parentheses). ^(d))Normalized modulus of elasticity relativeto competitive polypropylene nanocomposite (8a) processed under similarconditions (=1.0).

The elasticity modulus of samples is enhanced by 26 to 47% with respectto polypropylene without dispersing agent.

EXAMPLE 9 Preparation of Polypropylene Nanocomposites in a Batch MixerBased on Amine Modified Montmorillonite

The polypropylene nanocomposites are prepared in analogy to Example 7with the amine modified montmorillonite Nanofil 15® obtained from SuedChemie instead of montmorillonite clay [Cloisite (Na⁺)® obtained fromSouthern Clay Industries]. The results are summarized in Table 9.

TABLE 9 Example Dispersing agent d-001 in Å^(c)) 9a^(a)) none 28.59b^(b)) PODA-b-AN (3g) 35.3 9c^(b)) PODA-b-NVP (4b) 33.3 9d^(b))PODA-b-HEA (3f) 35.3 9e^(b)) PODA-b-VP (3h) 38.4 9f^(b)) PODA-b-PEGMEA(3i) 37.6 9g^(b)) PODA-b-PEO750 (5a) 34.6 9h^(b)) PODA-b-PEO1000 (5b)34.6 9i^(b)) PODA-b-VBTEAC (6a) 42.0 9j^(b)) PODA-b-VBTBPC (6b) 32.09k^(b)) PODA-b-VBDHEA (6c) 35.0 Explanation of footnotes a), b), c) seeend of Table 7.

The X-ray diffraction (XRD) spectra show that all acrylic polymersaccording to Table 4 intercalate the used day in the direct meltblending experiments in the batch mixer. This is shown by the d-spacingof 32-42 Å.

EXAMPLE 10 Preparation of Polypropylene Nanocomposites in a Batch MixerBased on Unmodified Sodium Montmorillonite

The polypropylene nanocomposites are prepared in analogy to Example 7with the polypropylene Basell HP400N® instead of Basell KY 6100®.However, the small scale injection moulding is performed with aCS-183MMX Minimax moulder. The mixing chamber is preheated to 250° C.and the mould is oven heated to 120° C. for one hour prior to injectionmoulding. Approximately 5 g of the material is placed in the mixingchamber and heated for 4 to 5 minutes. A small shot is taken from theCS-183MMX Minimax moulder prior to placing the mould in position. Sixtensile bars with the dimensions of central section 35 mm by 5 mm by 1mm (overall length 58 mm) are produced for each of the 5 g material.

Tensile testing is performed with a Instron tensile tester equipped witha 5000 N load cell (1 mm/min) and a 25 mm extensometer. The results aresummarized in Table 10.

TABLE 10 Normalized Modulus of Example Dispersing agent Elasticity^(d))10a^(a)) none 1.20 10b^(b)) PODA-co-DEGEEA (1f) 1.44 10c^(b))PODA-co-BA-co-DMAEA (1d) 1.34 10d^(b)) PODA-co-BA-co-MAH (1e) 1.3210e^(b)) PODA-co-PEGMEA (1g) 1.40 10f^(b)) PODA-co-PEGMEA (2b) 1.5510g^(b)) PODA-co-DMAEA (1c) 1.28 10h^(b)) PODA-co-DMAEA (2d) 1.40Explanation of footnotes a), b) and d) see end of Table 8.

The elasticity modulus of samples is enhanced by 28 to 55% with respectto polypropylene without dispersing agent.

EXAMPLE 11 Preparation of Polypropylene Nanocomposites in a Twin ScrewExtruder

Processing is carried out with a Japan Steel Works 30 mm diameter twinscrew extruder of L/D ratio 42 (JSW TEX 30) that comprises tentemperature controlled barrel sections each with L/D of 3.5, threeunheated sampling zones with L/D 1.167, and a cooled feed block with L/D3.5. The screw configuration consists of a combination of mixing,kneading and conveying elements familiar to those skilled in the art.Materials are fed into the extruder via a JSW TTF20 gravimetric feeder(Feed 1) and a K-Tron KQX gravimetric feeder (Feed 2). The JSW TEX 30 isoperated in a co-rotating (intermeshing self wiping) mode withthroughput of 10 kg/hr and a screw speed of 200 rpm. Vacuum venting isapplied to the final barrel section. The extrudate is cooled in a waterfilled strand bath and pelletized.

In a first step a 10 wt % clay masterbatch is prepared. Feed 1 comprisesa dry blend of polypropylene [Basell HP400N®] and a stabilizer which iscomposed of 0.1 wt % of Irganox 1010® (pentaerythritoltetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]) and 0.1 wt %of Irgafos 168® (tris(2,4-di-tert-butylphenyl)phosphite). Feed 2comprises a blend of the clay [Cloisite (Na⁺)® obtained from SouthernClay Industries] and the non-ionic surfactant in the ratio defined inTable 11. All barrel sections are heated to 170° C.

In the second step the masterbatch is let down to the required claylevel (see Table 4) by blending the masterbatch (Feed 2) with furtherpolypropylene plus stabilizer (Feed 1). The first barrel section isheated at 160° C. the remaining barrel sections are heated at 200° C.

Injection moulding of the extruded samples are preformed with aCincinnati Milacron VS55 28 mm diameter injection moulding machinecomprising four temperature controlled sections of L/D 23/1 heated at215-230° C. and a mould temperature of 40° C. The machine is operated ata clamp force of 50 tons and at a maximum injection pressure of 2005bar.

Tensile testing to obtain tensile modulus and tensile strength isperformed according to ISO 521 using an Instron 5500R material tensiletester equipped with a 5 kN load cell and a 50 mm extensometer. Thestrain rate is 1 mm/min. Properties are normalised tensile properties vspolypropylene=1.0. Elongation at break is measured with a strain rate of50 mm/min.

TABLE 11 Tensile Elongation Tensile Example Additive (2.5 wt %)Modulus^(d)) at break^(e)) Strength^(f)) 11a^(a)) no additive 1.17 1.01.06 11b^(b)) PODA-co-DEGEEA (1f) 1.22 3.1 1.11 11c^(b)) PODA-co-PEGMEA(2b) 1.26 1.3 1.11 11d^(b)) PODA-co-DMAEA (2d) 1.20 4.2 1.07 11e^(b))PODA-co-DMAEA (1c) 1.22 3.4 1.07 ^(a))Comparative Example. ^(b))Exampleaccording to the invention (number in parentheses). ^(d))Normalizedmodulus of elasticity relative to competitive polypropylenenanocomposite (11a) processed under similar conditions (=1.0).^(e))Normalized elongation at break relative to polypropylene processedunder similar conditions (=1.0). ^(f))Normalized tensile strengthrelative to polypropylene processed under similar conditions (=1.0).

EXAMPLE 12 Polypropylene Nanocomposites in a Twin Screw Extruder

The samples are prepared using process conditions similar to Example 11with the additive premixed with clay in (1:5 ratio) at 80° C. A 10% claymasterbatch is prepared in step 1.

TABLE 12 Tensile Elong. Tensile Impact Example Additive (wt %)Modulus^(d)) at break^(e)) Strength^(f)) Strength^(g)) 12a^(a)) noadditive 1.26 1.0 1.05 1.1 12b^(b))   1 wt % PODA-co-MAH 3:1 (1h) 1.183.6 1.03 1.3 12c^(b))   1 wt % PODA-co-MAH 5:1 (1i) 1.22 1.6 1.04 1.412d^(b))   1 wt % PODA-co-MAH (2j) 1.27 2.8 1.00 1.1 12e^(b))   1 wt %PODA-co-NVP (2c) 1.25 3.0 1.02 1.1 12f^(b))   1 wt % PODA-co-PEGMEA (2b)1.24 0.8 0.98 1.0 12g^(b)) 2.5 wt % PODA-co-MAH (2j) 1.18 3.5 0.99 1.1^(a))Comparative Example. ^(b))Example according to the invention(number in parentheses). ^(d))Normalized modulus of elasticity relativeto competitive polypropylene nanocomposite (12a) processed under similarconditions (=1.0). ^(e))Normalized elongation at break relative topolypropylene processed under similar conditions (=1.0). ^(f))Normalizedtensile strength relative to polypropylene processed under similarconditions (=1.0). ^(g))Normalized tensile impact strength relative topolypropylene processed under similar conditions (=1.0).

Samples with additives show Improvements in tensile modulus and impactstrength over PP and significant improvement in elongation at break overthe clay alone composite.

EXAMPLE 13 Polypropylene Nanocomposites in a Twin Screw Extruder

The samples are prepared using process conditions similar to Example 11with the additive premixed with clay in (1:5 ratio) at 80° C. A 10% claymasterbatch is prepared in step 1 two different clays are used Cloisite(Na⁺)® obtained from Southern Clay Industries and Somasif ME100®obtained from Co-op Chemical Company Japan.

TABLE 13 Tens. Elong. Tensile Example 5% Clay Additive (1 wt %)Mod.^(d)) at break^(e)) Strength^(f)) 13a^(a)) Cloisite Na+ No additive1.17 1.0 1.05 13b^(b)) Cloisite Na+ PODA-co-MMA-co-MAH 1.12 6.5 1.00(2f) 13c^(b)) Somasif ME100 No additive 1.16 1.6 1.04 13d^(b)) SomasifME100 PODA-co-MMA-co-MAH 1.12 3.9 1.01 (2f) ^(a))Comparative Example.^(b))Example according to the invention (number in parentheses).^(d))Normalized modulus of elasticity relative to competitivepolypropylene nanocomposite (13a) processed under similar conditions(=1.0). ^(e))Normalized elongation at break relative to polypropyleneprocessed under similar conditions (=1.0). ^(f))Normalized tensilestrength relative to polypropylene processed under similar conditions(=1.0).

Samples with additives show Improvements in tensile strength and modulusover PP and marked improvement in elongation at break over clay alonecomposites.

EXAMPLE 14 Polypropylene Nanocomposites in a Twin Screw Extruder

The samples were prepared using process conditions similar to Example 11with the additive premixed with clay in (1:5 ratio) at ambienttemperature. A 10% clay masterbatch is prepared in step 1.

TABLE 14 Tens. Elong. Tensile Examp. 5% Clay Additive (1 wt %) Mod.^(d))at break^(e)) Strength^(f)) 14a^(a)) No clay No additive 1.0 — 1.0 14b^(b)) Cloisite Na+ No additive 1.14 1.0 1.01 14c^(b)) Cloisite Na+PODA (4a) 1.14 2.8 0.98 14d^(b)) Cloisite Na+ PODA-co-PDMAEA (2d) 1.135.7 0.98 14e^(b)) Cloisite Na+ PODA-b-PDMAEA 5000 (4e) 1.13 3.2 0.9614f^(b)) Cloisite Na+ PODA-co-PDMAEA 15000 (4d) 1.13 3.6 0.96^(a))Comparative Example. ^(b))Example according to the invention(number in parentheses). ^(d))Normalized modulus of elasticity relativeto competitive polypropylene nanocomposite (14b) processed under similarconditions (=1.0). ^(e))Normalized elongation at break relative topolypropylene processed under similar conditions (=1.0). ^(f))Normalizedtensile strength relative to polypropylene processed under similarconditions (=1.0).

Samples with additives show Improvements in tensile strength and modulusover PP and marked improvement in elongation at break over clay alonecomposites. PODA by itself gives good tensile property improvements.

EXAMPLE 15 Polypropylene Nanocomposites in a Twin Screw Extruder

The samples are prepared using process conditions similar to Example 11with the additive premixed with clay in (1:5 ratio) at ambienttemperature. A 10% clay masterbatch is prepared in step 1.

TABLE 15 Examp. Clay Additive T.M.^(d)) E at b.^(e)) T.S.^(f)) 15a^(a))No clay No additive 1.0 — 1.0 15b^(b)) 5% Cloisite Na+ No additive 1.241.0 1.07 15c^(b)) 1% Cloisite Na+ 0.2 wt % PODA-co-MAH (2d) 1.11 13.91.04 15d^(b)) 3% Cloisite Na+  .6% PODA-co-MAH (2d) 1.24 7.1 1.0615e^(b)) 5% Cloisite Na+   1% PODA-co-MAH (2d) 1.25 5.2 1.06 15f^(b)) 5%Cloisite Na+ 1.25% PODA-co-MAH (2d) 1.24 3.7 1.04 15g^(b)) 5% CloisiteNa+  0.5% PODA-co-MAH (2d) 1.23 5.6 1.05 15h^(b)) 1% Cloisite Na+  0.2%PODA-co-MAH (1h) 1.11 15.1 1.02 15i^(b)) 3% Cloisite Na+  0.6%PODA-co-MAH (1h) 1.16 11.7 1.03 15j^(b)) 5% Cloisite Na+   1%PODA-co-MAH (1h) 1.20 4.0 1.03 15k^(b)) 5% Cloisite Na+ 1.25%PODA-co-MAH (1h) 1.18 5.7 1.02 15l^(b)) 5% Cloisite Na+  0.5%PODA-co-MAH (1h) 1.23 5.6 1.05 15m^(b)) 1% Cloisite Na+  0.2 wt %PODA-co-NVP (2c) 1.11 17.7 1.02 15n^(b)) 3% Cloisite Na+  .6%PODA-co-NVP (2c) 1.16 8.4 1.01 15o^(b)) 5% Cloisite Na+   1% PODA-co-NVP(2c) 1.22 5.6 1.03 15p^(b)) 5% Cloisite Na+ 1.25% PODA-co-NVP (2c) 1.176.9 0.99 15q^(b)) 5% Cloisite Na+  0.5% PODA-co-NVP (2c) 1.15 7.2 1.01^(a))Comparative Example. ^(b))Example according to the invention(number in parentheses). ^(d))Normalized modulus of elasticity relativeto competitive polypropylene nanocomposite (15b) processed under similarconditions (=1.0). ^(e))Normalized elongation at break relative topolypropylene processed under similar conditions (=1.0). ^(f))Normalizedtensile strength relative to polypropylene processed under similarconditions (=1.0).

Samples with additives show Improvements in tensile strength and modulusover PP and marked improvement in elongation at break over clay alonecomposites. Significant improvements over PP are seen with very low dayadditive levels.

EXAMPLE 16 Polypropylene Nanocomposites in a Twin Screw Extruder

The samples are prepared using process conditions similar to Example 11with the additive premixed with clay in (1:5 ratio) at ambienttemperature. A 10% clay masterbatch is prepared in step 1.

TABLE 16 Examp. Clay Additive (wt %) T.M.^(d)) E. at b.^(e)) T.S.^(f))16a^(a)) No clay No additive 1.0 — 1.0 16b^(b)) 5% Cloisite Na+ Noadditive 1.22 1.0 1.04 16c^(b)) 5% Cloisite Na+ 1% Tegomer DA100N^(h))1.23 2.6 1.04 16d^(b)) 5% Cloisite Na+ 1% PODA-co-NVP (1k) 1.20 2.4 1.0216e^(b)) 5% Cloisite Na+ 1% PODA-co-NVP (1I) 1.24 3.6 1.02 16f^(b)) 5%Cloisite Na+ 1% PODA-co-NVP (1n) 1.24 3.2 1.02 16g^(b)) 3% Cloisite Na+0.6% PODA-co-NVP (1n) 1.13 4.4 1.00 16h^(b)) 1% Cloisite Na+ 0.2%PODA-co-NVP (1n) 1.06 12.6  0.99 16i^(b)) 5% Cloisite Na+ 0.5%PODA-co-NVP (1n) 1.18 4.0 1.00 16j^(b)) 5% Cloisite Na+ 1.25%PODA-co-NVP (1l) 1.17 1.1 0.98 16k^(b)) 5% Cloisite Na+ 1% PODMA-co-NVP(1m) 1.20 3.2 1.02 16l^(b)) 5% Cloisite Na+ 1% PODMA-co-MAH (1o) 1.225.3 1.02 16m^(b)) 5% Somasif ME100 1% PODA-co-MAH (1i) 1.24 6.7 1.02^(a))Comparative Example. ^(b))Example according to the invention(number in parentheses). ^(d))Normalized modulus of elasticity relativeto competitive polypropylene nanocomposite (14b) processed under similarconditions (= 1.0). ^(e))Normalized elongation at break relative topolypropylene processed under similar conditions (= 1.0) ^(f))Normalizedtensile strength relative to polypropylene processed under similarconditions (= 1.0). ^(h))RTM product of Goldschmidt.

Samples with additives show Improvements in tensile strength and modulusover PP and marked improvement in elongation at break over clay alonecomposites. Significant improvements over PP are seen with very low clayadditive levels.

EXAMPLE 17 Polypropylene Nanocomposites in a Twin Screw Extruder

The samples are prepared using process conditions similar to Example 11with the additive premixed with day in (1:5 ratio) at ambienttemperature. A 10% clay masterbatch is prepared in step 1.

TABLE 17 Clay E. at Example (5 wt %) Additive (1 wt %) T.M.^(d)) b^(e))T.S.^(f)) 17a^(a)) No clay No additive 1.0 — 1.0 17b^(b)) Cloisite Na+No additive 1.18 1.0 1.02 17c^(b)) Cloisite Na+ PODA-co-GA (1q) 1.12 3.20.99 17d^(b)) Cloisite Na+ PODA-co-MEP (2m) 1.14 4.4 1.01 17e^(b))Cloisite Na+ PLA-co-MAH (2n) 1.15 3.7 1.00 17f^(b)) Cloisite Na+PODA-co-GMA (2n) 1.15 3.7 1.01 ^(a))Comparative Example. ^(b))Exampleaccording to the invention (number in parentheses). ^(d))Normalizedmodulus of elasticity relative to competitive polypropylenenanocomposite (17b) processed under similar conditions (= 1.0).^(e))Normalized elongation at break relative to polypropylene processedunder similar conditions (= 1.0). ^(f))Normalized tensile strengthrelative to polypropylene processed under similar conditions (= 1.0).

EXAMPLE 18 Polypropylene Nanocomposites in a Twin Screw Extruder

The samples are prepared using process conditions similar to Example 11with the additive premixed with clay in (1:5 ratio) at ambienttemperature. A 10% clay masterbatch is prepared in step 1.

TABLE 18 E. at Example Clay (5 wt %) Additive (wt %) T.M.^(d)) b.^(e))T.S.^(f)) 18a^(a)) No clay^(d) No additive 1.0 — 1.0 18b^(b)) CloisiteNa+^(d) No additive 1.18 1.0 1.02 18c^(b)) Cloisite Na+^(e) 1%PODA-co-HAH 1.28 2.1 1.09 (2e) 7.5% Polybond 3200 18d^(b)) Cloisite20A^(d) no additive 1.20 1.2 1.04 18e^(b)) Cloisite 20A^(d) 7.5%Polybond 1.41 0.6 1.14 3200 ^(a))Comparative Example. ^(b))Exampleaccording to the invention (number in parentheses). ^(d))Normalizedmodulus of elasticity relative to competitive polypropylenenanocomposite (18b) processed under similar conditions (= 1.0).^(e))Normalized elongation at break relative to polypropylene processedunder similar conditions (= 1.0). ^(f))Normalized tensile strengthrelative to polypropylene processed under similar conditions (= 1.0).

The Examples according to the invention show a significant imrpovementin the elongation at break.

EXAMPLE 19 Thermal Stability Under Air and Nitrogen of PolypropyleneNanocomposites

The following data demonstrate that samples prepared with a copolymeradditives according to the invention have significantly greater thermalstability under air than either polypropylene or polypropylene plusunmodified day with the temperature for maximum weight loss approx 30°C. higher.

The samples (˜10 mg, cryoground powder) are heated from 50 to 500° C. at10° C./min in a Mettler thermobalance T6A/SDTA851 equipped with a T50801 sample robot under air or under nitrogen atmosphere. Onset and endtemperatures are calculated by the tangent method. The results aresummarized in Table 19.

TABLE 19 Data from thermogravimetric analysis under air ofnanocomposites with 5 wt % Cloisite Na+ Exam- Residual ple MaterialT_(onset) ° C. T_(end) ° C. T_(max) ° C. weight, % 19a^(a))Polypropylene 280 390 380 0.6 19b^(a)) No copolymer 269 388 381 6.119c^(b)) 1% POOA-co- 287 422 416 6.2 MAH 1j) 19d^(b)) 1% PODA-co- 285419 413 5.6 NVP 1k) ^(a))Comparative Example. ^(b))Example according tothe invention.

EXAMPLE 20 Plate-and-Plate Oscillatory Rheology

The viscosity of the samples is similar to polypropylene (see Table 20).Conventional organic modified clays and derived nanocomposites havesignificantly increased viscosity with respect to polypropylene. Clayalone composites have a reduced viscosity (see comparative Example inTable 20). The nanocomposites of the present invention are more readilyprocessed than conventional nanocomposites based on organic modifiedclays.

The melt behavior of the blends and neat components in the low shearrate range is studied using a dynamic rheometer ARES (AdvancedRheometric Expansion Systems). Measurements are performed in theplate-plate configuration with a gap of 1.5 to 2.0 mm. Specimens aredisks with diameter of 25 mm cut from the approximately 2 mm thicksheets prepared by compression molding. Frequency sweep experiments areperformed on each of the materials over a frequency range of 0.1 to 100rad/s, with data collected at five points per decade. Temperature of theexperiments is set at 200° C., corresponding to the temperature of thecomposite preparation. The results are summarized in Table 20.

TABLE 20 Complex Viscosity, Pa · s @ 200° C. Cloisite for frequency[rad/sec] Example Na+ Copolymer 0.1 1.0 10 100 20a^(a)) none none 31602340 1171 395 20b^(a)) 5% none 2986 1944 939 312 20c^(b)) 5% PODA-co-MAH(1h) 3181 2317 1175 403 20d^(b)) 5% PODA-co-MAH (1i) 3276 2353 1181 40320e^(b)) 5% PODA-co-MAH (2j) 3191 2285 1145 390 ^(a))ComparativeExample. ^(b))Example according to the invention.

1. A composition comprising (a) a synthetic polymer, (b) a natural orsynthetic phyllosilicate filler or a mixture of such phyllosilicatefillers, and (c) as dispersing agent an acrylic copolymer containing analkyl acrylate or methacrylate comprising at least 8 methylene groups inthe side chain.
 2. A composition according to claim 1, wherein component(c) is a statistical, block or comb copolymer having at least onehydrophilic and at least one hydrophobic segment which is based on analkyl acrylate according to claim
 1. 3. A composition according to claim1, wherein component (a) is a polyolefin.
 4. A composition according toclaim 1, wherein component (b) is a nanoparticulate filler.
 5. Acomposition according to claim 1, wherein component (b) is ananoparticulate filler which is not organically modified.
 6. Acomposition according to claim 1, wherein component (b) is a layeredsilicate clay.
 7. A composition according to claim 1, wherein component(b) is a montmorillonite, bentonite, beidelite, mica, hectorite,saponite, nontronite, sauconite, vermiculite, ledikite, magadite,kenyaite, stevensite, volkonskoite, hydrotalcite, illite, kaolinite,wollastonite, attapulgite, talc or silica or a mixture thereof.
 8. Acomposition according to claim 1, wherein the long chain alkylmeth(acrylate) segment in component (c) contains a C₁₂-C₃₂alkylmeth(acrylate).
 9. A composition according to claim 1, wherein component(c) is ) is poly(octadecyl acry-late)-co-(maleic anhydride),poly(octadecyl acrylate)-co-(poly(ethylene glycol) methyl etheracrylate), poly(octadecyl acrylate)-co-(diethylene glycol ethyl etheracrylate), poly(octadecyl acrylate)-co-(N-vinylpyrrolidone),poly(octadecyl methacrylate)-co-(N-vinylpyrrolidone), poly(octadecylmethacrylate)-co-(maleic anhyd ride), poly(octadecylacrylate)-co-(glycidyl acrylate), poly(octadecylacrylate)-co-(2-dimethylaminoethyl acrylate), poly(octadecylacrylate)-co-(poly(ethylene glycol) methyl ether acrylate),poly(octadecyl acrylate)-co-(d iethylene g lycol ethyl ether acrylate),poly(octadecyl acrylate)-co-(methacrylolyoxyethyl phosphate),poly(lauryi acrylate)-co-(maleic anhydride), poly(octadecylacrylate)-co-(glycidyl methacrylate) or poly(octadecylacrylate)-co-(methacrylic acid).
 10. A composition according to claim 1,wherein component (b) is present in an amount of from 0.1 to 40%, basedon the weight of component (a).
 11. A composition according to claim 1,wherein component (c) is present in an amount of from 0.1 to 20%, basedon the weight of component (a).
 12. A composition according to claim 1,comprising in addition, besides components (a), (b) and (c), furtheradditives.
 13. A composition according to claim 12, comprising asfurther additives phenolic antioxidants, light-stabilizers, processingstabilizers, solvents, pigments, dyes, plasticizers, compatibilizers,toughening agents, thixotropic agents and/or metal deactivators.
 14. Acomposition according to claim 1 in the form of a masterbatch orconcentrate comprising component (a) in an amount of from 5 to 90%,component (b) in an amount of from 5 to 80%, and component (c) in anamount of from 1 to 50% by weight.
 15. A process for the preparation ofa composition according to claim 1 which process comprises melt mixing amixture of components (a), (b) and (c).
 16. A process according to claim15, wherein the melt mixing occurs between 120 and 290° C.
 17. Acomposition obtained by the process according to claim
 15. 18. Anarticle comprising the composition according to claim 1.